Substrate processing method, storage medium storing program for executing substrate processing method and substrate processing apparatus

ABSTRACT

There is provided a substrate processing method capable of preventing pattern collapse when a rinse solution is removed from a substrate on which a microscopic resist pattern is formed and also capable of reducing cost for processing the substrate by decreasing an amount of usage of a hydrophobicizing agent. The substrate processing method includes a rinse solution supply process (step S 12 ) for supplying the rinse solution onto the substrate on which the resist pattern is formed; and a rinse solution removing process (steps S 14  to S 16 ) for removing the rinse solution from the substrate in an atmosphere including vapor of a first processing solution that hydrophobicizes the resist pattern.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of Japanese Patent Application No.2009-295390 filed on Dec. 25, 2009, the entire disclosures of which areincorporated herein by reference.

FIELD OF THE INVENTION

The present disclosure relates to a substrate processing method forprocessing a substrate by using a processing solution, a storage mediumstoring a program for executing the substrate processing method and asubstrate processing apparatus for performing the substrate processingmethod.

BACKGROUND OF THE INVENTION

In a photolithography process for manufacturing a semiconductor device,photoresist is coated on a surface of a semiconductor substrate(hereinafter, simply referred to as a “substrate” or a “wafer”), and amask pattern is exposed on the photoresist and then is developed, sothat a resist pattern is formed on the surface of the wafer.

In such a photolithography process, a developing process may beperformed by, e.g., a puddle method or a dipping method. By way ofexample, in the puddle method, the developing process is performed bysupplying a developing solution to the wafer, whereas in the dippingmethod, the developing process is performed by submerging the wafer inthe developing solution. Then, in both methods, a rinse solution such aspure water which is used as a cleaning solution is supplied to the waferto wash away the developing solution. Thereafter, to remove the rinsesolution from the wafer, a drying process is performed by blowing air tothe wafer or by rotating the wafer.

Meanwhile, along with the recent trend for higher degree ofminiaturization of semiconductor devices, resist patterns are gettingfiner and becoming to have a higher aspect ratio. Since such resistpatterns are microscopic and have a high aspect ratio, when the rinsesolution is removed from between the patterns during the drying process,an attraction force may be generated between the patterns due to asurface tension of the rinse solution, thereby resulting in a so-called“pattern collapse”. In order to prevent the pattern collapse, there hasbeen proposed a developing method for supplying, onto a substrate, anorganic solvent having a smaller surface tension than that of the rinsesolution before the drying process is performed.

By way of example, in order to prevent pattern collapse in the processof removing a rinse solution, there has been proposed a developingmethod for supplying a rinse solution to a substrate having a developedresist pattern and supplying a fluorine-containing organic solvent tothe substrate onto which the rinse solution has been supplied (see, forexample, Patent Document 1).

-   Patent Document 1: Japanese Patent Laid-open Publication No.    2003-178943

However, when a processing solution containing the organic solvent issupplied to the substrate onto which the rinse solution has beensupplied, the following problems may be caused.

As a next-generation exposure technology, EUV (Extreme Ultra-Violet)exposure is under development, and further miniaturization of a resistpattern is progressing. Besides, when an etching is performed using theminiaturized resist pattern as a mask to transfer the resist patternonto an etching target film under the resist pattern, there may be acase in which a height of a resist pattern is increased depending onetching conditions. If the height of the resist pattern increases, anaspect ratio with respect to a width of the resist pattern may also beincreased. Such an increase of the aspect ratio of the resist patternmay cause pattern collapse depending on a relationship between a surfacetension of pure water and a contact angle of the pure water with respectto the resist pattern, when the water is removed from the resist patternduring the drying process after the developing process and the rinseprocess.

It has been attempted to prevent pattern collapse by hydrophobicizing asurface of a resist pattern through the use of a hydrophobicizing agentinstead of the processing solution including the fluorine-containingorganic solvent. Since, however, the hydrophobicizing solution is ahigh-price liquid chemical, cost for processing the substrate may beincreased.

Furthermore, the pattern collapse may occur not only in the developingprocess but also in various subsequence substrate processes performedafter the resist pattern is developed. For example, the pattern collapsemay occur in a cleaning process for cleaning the substrate on which theresist pattern is formed.

BRIEF SUMMARY OF THE INVENTION

In view of the foregoing, the present disclosure provides a substrateprocessing method capable of preventing pattern collapse when a rinsesolution is removed from a substrate on which a microscopic resistpattern is formed and also capable of reducing cost for processing thesubstrate by decreasing an amount of usage of a hydrophobicizing agent.

To solve the aforementioned problems, the following means have beendevised in accordance with the present disclosure.

In accordance with one aspect of the present disclosure, there isprovided a substrate processing method including: a rinse solutionsupply process for supplying a rinse solution onto a substrate on whicha resist pattern is formed; and a rinse solution removing process forremoving the rinse solution from the substrate in an atmosphereincluding vapor of a first processing solution that hydrophobicizes theresist pattern.

In accordance with another aspect of the present disclosure, there isprovided a substrate processing apparatus including: a substrate holderthat holds a substrate on which a resist pattern is formed; a rinsesolution supply unit that supplies a rinse solution onto the substrateheld by the substrate holder; a vapor supply unit that supplies vapor ofa first processing solution, which hydrophobicizes the resist pattern,onto the substrate on which the rinse solution is supplied from therinse solution supply unit; and a rinse solution removing unit thatremoves the rinse solution from the substrate in an atmosphere includingthe vapor of the first processing solution supplied from the vaporsupply unit.

In accordance with the present disclosure, pattern collapse can beprevented when a rinse solution is removed from a substrate on which amicroscopic resist pattern is formed, and cost for processing thesubstrate can be reduced by decreasing an amount of usage of ahydrophobicizing agent.

BRIEF DESCRIPTION OF THE DRAWINGS

Non-limiting and non-exhaustive embodiments will be described inconjunction with the accompanying drawings. Understanding that thesedrawings depict only several embodiments in accordance with thedisclosure and are, therefore, not to be intended to limit its scope,the disclosure will be described with specificity and detail through useof the accompanying drawings, in which:

FIG. 1 is a plane view of a coating and developing system including adeveloping apparatus in accordance with a first embodiment of thepresent disclosure;

FIG. 2 is a front view of the coating and developing system shown inFIG. 1;

FIG. 3 is a rear view of the coating and developing system shown in FIG.1;

FIG. 4 is a plane view of a developing unit in accordance with the firstembodiment;

FIG. 5 is a cross sectional view of the developing unit shown in FIG. 4;

FIG. 6 is a diagram schematically illustrating major parts of thedeveloping unit in accordance with the first embodiment;

FIG. 7 provides a flowchart for describing a process sequence of adeveloping method using the developing unit;

FIGS. 8A to 8D are first side views for illustrating respectiveprocesses of the developing method using the developing unit;

FIGS. 9A to 9D are second side views for illustrating respectiveprocesses of the developing method using the developing unit;

FIGS. 10A to 10D are third side views for illustrating respectiveprocesses of the developing method using the developing unit;

FIG. 11 is a fourth side view for illustrating respective processes ofthe developing method using the developing unit;

FIG. 12 is a diagram for describing a relationship between a contactangle of a rinse solution and a force applied to collapse patterns whenthe rinse solution exists between the patterns;

FIG. 13 is a diagram for describing a reaction mechanism in ahydrophobicizing process in which a first processing solution includingTMSDMA hydrophobicizes a surface of a resist pattern;

FIG. 14 is a cross sectional view illustrating a developing unit inaccordance with a first modification example of the first embodiment;

FIGS. 15A to 15E are schematic diagrams for illustrating a principle ofa method for detecting a position of an interface between a rinsesolution and an atmosphere;

FIG. 16 is a schematic diagram illustrating major parts of a developingunit in accordance with a second modification example of the firstembodiment;

FIG. 17 is a flowchart for describing a process sequence of a developingmethod using the developing unit in accordance with the secondmodification example of the first embodiment;

FIG. 18 is a schematic diagram illustrating major parts of a developingunit in accordance with a second embodiment of the present disclosure;

FIG. 19 is a perspective view illustrating an example vapor supplynozzle provided with a strip-shaped discharge opening;

FIG. 20 is a flowchart for describing a process sequence of thedeveloping method using the developing unit in accordance with thesecond embodiment;

FIGS. 21A to 21D are side views for illustrating respective processes ofthe developing method using the developing unit in accordance with thesecond embodiment;

FIGS. 22A and 22B are plane views for illustrating respective processesof the developing method using the developing unit in accordance withthe second embodiment;

FIG. 23 is a schematic diagram illustrating major parts of a developingunit in accordance with a third embodiment of the present disclosure;

FIGS. 24A and 24B are enlarged views of a nozzle unit;

FIG. 25 is a flowchart for describing a process sequence of a developingmethod using the developing unit in accordance with the thirdembodiment;

FIG. 26 is a schematic side view illustrating major parts of adeveloping unit in accordance with a fourth embodiment of the presentdisclosure;

FIG. 27 is a plane view schematically illustrating a vapor supplynozzle; and

FIG. 28 is a flowchart for describing a process sequence of a developingmethod using the developing unit in accordance with the fourthembodiment.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, embodiments of the present disclosure will be describedwith reference to the accompanying drawings.

First Embodiment

Referring to FIGS. 1 to 13, a developing apparatus and a developingmethod in accordance with a first embodiment of the present disclosurewill be explained. The developing apparatus and the developing method inaccordance with the first embodiment are related to examples in which asubstrate processing apparatus and a substrate processing method inaccordance with the present disclosure are applied to a developingapparatus and a developing method, respectively.

FIGS. 1 to 3 are diagrams illustrating an entire configuration of acoating and developing system including the developing apparatus inaccordance with the first embodiment. FIGS. 1 to 3 are a plane view, afront view and a rear view thereof, respectively.

The coating and developing system 1 includes a cassette station 10, aprocessing station 11 and an interface section 12 connected as one body.The cassette station 10 loads a plurality of, e.g., 25 sheets ofsemiconductor wafers W as processing target substrates into a wafercassette CR of the coating and developing system from the outside andthe cassette station 10 unloads them from the wafer cassette CR to theoutside. Further, the cassette station 10 also loads and unloads thewafers W into and from the wafer cassette CR. In the processing station11, various processing units for performing single-wafer processesduring a coating and developing process are arranged at preset positionsin multi levels. The interface section 14 transfers the wafers W betweenthe processing station 11 and an exposure apparatus (not shown) adjacentto the processing station 11.

As shown in FIG. 1, the cassette station 10 may include a cassettemounting table 20 and a wafer transfer device 21. A plurality of, e.g.,four wafer cassettes CR may be arranged at positions of protrusions 20 aon the cassette mounting table 20 in a row in an X direction such thattheir respective wafer loading/unloading openings face the processingstation 11. The wafer transfer device 21 is configured to be movable ina cassette arrangement direction (X direction) and also movable in anarrangement direction (Z direction) of the wafers accommodated in thewafer cassette CR. The wafer transfer device 21 is capable ofselectively accessing the respective wafer cassettes CR. Further, thewafer transfer device 21 is rotatable in a θ direction and is alsocapable of accessing an alignment unit ALIM and an extension unit EXTincluded in a third unit set G3 of the processing station 12 to bedescribed later.

As depicted in FIG. 1, a main wafer transfer mechanism 22 movable in avertical direction is provided in a central portion of the processingstation 11, and a single set or multiple sets of processing units areall arranged around the main wafer transfer mechanism 22 in multilevels. In the present embodiment, five unit sets G1 to G5 are arrangedin multi levels. Multi-level units of the first unit set G1 and thesecond unit set G2 are arranged on the front side of the coating anddeveloping system (front side of FIG. 1). Multi-level units of the thirdunit set G3 are arranged adjacent to the cassette station 10, whilemulti-level units of the fourth unit set G4 are arranged adjacent to theinterface section 12. Further, multi-level units of the fifth unit setG5 are arranged on the rear side of the coating and developing system.The fifth unit set G5 is configured to be movable along rails 25 for themaintenance of the main wafer transfer mechanism 22.

As depicted in FIG. 3, the main wafer transfer mechanism 22 may includea wafer transfer device 46 that is configured to be movable up and downin a vertical direction (Z direction). A cylindrical support 49 isconnected with a rotation shaft of a motor (not shown). The cylindricalsupport 49 is made to rotate as one body with the wafer transfer device46 about the rotation shaft by a rotational driving force of the motor.Accordingly, the wafer transfer device 46 is rotatable in a θ direction.The wafer transfer device 46 may include a transfer arm 48.

As shown in FIG. 2, in the first unit set G1, two spinner typeprocessing units for processing wafers W mounted on spin chucks withincups CP, e.g., a resist coating unit COT and a developing unit DEV inaccordance with the first embodiment are stacked in two levels insequence from the bottom. In the second unit set G2, two spinner typeprocessing units, e.g., a resist coating unit COT and a developing unitDEV are stacked in two levels in sequence from the bottom. Sincedischarge of a resist solution and maintenance thereof is mechanicallytroublesome in the resist coating unit COT, it may be desirable to placethe resist coating unit COT in a lower level. However, if necessary, theresist coating unit COT may be positioned in an upper level.

Further, in an empty space below the first unit set G1 and the secondunit set G2 in the Z direction, a chemical container 13 for supplyingvarious processing solutions into the resist coating units COT and thedeveloping units DEV may be provided.

As illustrated in FIG. 3, in the third unit set G3, oven type processingunits for performing preset processes on wafers W mounted on mountingtables, e.g., a cooling unit COL, an adhesion unit AD, an alignment unitALIM, an extension unit EXT, prebaking units PAB and post exposurebaking units PEB are stacked in sequence from the bottom. Further, inthe fourth unit set G4, oven type processing units, e.g., a cooling unitCOL, an extension/cooling unit EXTCOL, an extension unit EXT, a coolingunit COL, prebaking units PAB and post exposure baking units PEB arestacked in sequence from the bottom. Further, a post baking unit forheating the wafers W after a developing process may be provided.

In the above-described configuration, the cooling units COL and theextension/cooling unit EXTCOL having low processing temperatures arearranged in lower levels, while the prebaking units PAB and the postexposure baking units PEB having high processing temperatures arearranged in upper levels. With this vertical arrangement, thermalinterference between the units can be reduced. However, these units maybe randomly arranged in multi levels.

The interface section 12 may have the same size as that of theprocessing station 11 in a depth direction but may have a smaller sizethan that of the processing station 11 in a widthwise direction. Aportable pickup cassette PU and a stationary buffer cassette BR arearranged in two levels on the front side of the interface section 12,and a peripheral exposure device 23 is provided on the rear side of theinterface section 12. Further, a wafer transfer device 24 is installedin a central portion of the interface section 12. The wafer transferdevice 24 is movable in X and Z directions and is capable of accessingthe two cassettes PU and BR and the peripheral exposure device 23.Further, the wafer transfer device 24 is rotatable in a θ direction andis capable of accessing the extension unit EXT of the fourth unit set G4in the processing station 11 as well as a wafer transfer table (notshown) of the exposure apparatus (not shown) adjacent to the interfacesection 12.

FIGS. 4 and 5 are a plane view and a cross sectional view of adeveloping unit in accordance with the first embodiment. In a centralportion of a developing unit DEV, an annular cup CP is provided within aprocessing chamber 25 of which atmosphere is capable of being controlledto be different from an external atmosphere. In order to prevent leakageof vapor of a first processing solution to the outside, as will bedescribed later, the inside of the processing chamber 25 may beadjustable to a negative pressure. Further, the cup CP is configured toallow the transfer arm 48 of the wafer transfer device 46 to be movedback and forth. A spin chuck 52 for horizontally holding the wafer Wthereon is provided within the cup CP. The spin chuck 52 is rotated bydriving motor 54 while the wafer W is held on the spin chunk 52 byvacuum attraction. The driving motor 54 is provided in an opening 50 aformed in a unit bottom plate 50 so as to be movable up and down and iscoupled to an elevation driving unit 60 composed of an air cylinder andan elevation guiding unit 62 via a cap-shaped flange 58 made ofaluminum. By this elevating mechanism, the wafer W can be transferredfrom and to the main wafer transfer mechanism 22.

Further, the spin chuck 52 serves as a substrate holder in accordancewith the present disclosure, and the driving motor 54 serves as arotating unit and a rinse solution removing unit in accordance with thepresent disclosure.

As illustrated in FIG. 5, a developing solution nozzle 36 for supplyinga developing solution onto a surface of the wafer W accommodated in thecup CP from above the wafer W is fixed at a leading end of a nozzle scanarm 37. A supply pipe 31 a is connected with the developing solutionnozzle 36, and the developing solution is supplied through the supplypipe 31 a by a developing solution supply mechanism 31. The developingsolution nozzle 36 has an elongated shape and is provided with, e.g., amultiple number of hole-shaped or slit-shaped supply openings throughwhich the developing solution is supplied. The nozzle scan arm 37 isfixed at an upper end of a vertical supporting member 40 which isconfigured to be horizontally movable in one direction (Y direction) ona guide rail 38 installed on the unit bottom plate 40. The nozzle scanarm 37 is configured to be movable in a Y direction as one body with thevertical supporting member 40 by a non-illustrated Y-direction drivingmechanism. Furthermore, the nozzle scan arm 37 is also configured to bemovable in a Z direction along the vertical support member 40, so that adistance between the developing solution nozzle 36 and the wafer W heldon the spin chuck 52 can be adjusted.

Further, a rinse nozzle 15, held by a nozzle holder 27, for supplying arinse solution onto the surface of the wafer W is installed so as to bemovable in the Y direction along the guide rail 38 by a nozzle scan arm17 and a vertical supporting member 26, as in the case of the developingsolution nozzle 36. A supply pipe 32 a is connected with the rinsenozzle 15, and the rinse solution is supplied from a rinse solutionsupply mechanism 32 through the supply pipe 32 a. Here, the rinsesolution may be, for example, pure water. The nozzle scan arm 17 is alsoconfigured to be movable along the vertical supporting member 26, sothat a distance between the rinse nozzle 15 and the wafer W held on thespin chuck 52 can be adjusted.

Further, the rinse nozzle 15 serves as a rinse solution supply unit inaccordance with the present disclosure.

Adjacent to the cup CP, a vapor supply nozzle 16, held by a nozzleholder 28, is fixed at a leading end of a nozzle scan arm 18, and thevapor supply nozzle 16 supplies vapor of a first processing solutionincluding a hydrophobicizing agent for hydrophobicizing a surface of aresist pattern 29 on the wafer W. The nozzle scan arm 18 is rotatableabout a motor 19 in a θ direction by being driven by the motor 19. Asupply pipe 33 a is connected with the vapor supply nozzle 16, and thevapor of the first processing solution is supplied from a vapor supplymechanism 33 through the supply pipe 33 a.

Further, the vapor supply nozzle 16 and the motor 19 serves as a vaporsupply unit and a moving unit in accordance with the present disclosure,respectively.

A liquid drain pipe 57 for draining the developing solution and therinse solution supplied onto the wafer is provided in a bottom of thecup CP, and the developing solution and the rinse solution are drainedto the non-illustrated outside of the system. Further, also installed inthe bottom of the cup CP is a gas exhaust pipe 59 for exhausting anatmosphere within the cup CP such as mist generated by the supply of thedeveloping solution or the processing solution. Typically, during theoperation, the atmosphere within the cup CP continues to be exhausted bya vacuum pump 51.

Moreover, a temperature sensor 64 for measuring a temperature of the cupCP and a temperature control heater for controlling the temperature ofthe cup CP are installed at the cup CP. Usually, the temperature controlheater 65 controls the temperature of the entire cup CP to be a presetvalue, e.g., about 23° C. or thereabout.

In the same way, a temperature sensor 66 for measuring a temperature ofthe gas exhaust pipe 59 and a temperature control heater 68 forcontrolling the temperature of the gas exhaust pipe 59 are installed atthe gas exhaust pipe 59, and a temperature sensor 67 for measuring atemperature of the liquid drain pipe 57 and a temperature control heater69 for controlling the temperature of the liquid drain pipe 57 areinstalled at the liquid drain pipe 57.

The developing solution supply mechanism 31, the rinse solution supplymechanism 32 and the vapor supply mechanism 33 supply the developingsolution, the rinse solution and the vapor of the first processingsolution to the developing solution nozzle 36, the rinse nozzle 15 andthe vapor supply nozzle 16, respectively, in response to instructions ofa controller 30. Further, the controller 30 controls timing for thesupply of the developing solution, the rinse solution and the vapor ofthe first processing solution and sends an instruction to a motorcontroller 34 for controlling a rotation speed of the driving motor 54to thereby control an overall process of the developing unit.

The controller 30 may have a non-illustrated storage composed of acomputer readable storage medium (recording medium) that stores aprogram for executing each process of a developing method in the coatingand developing system. The storage medium may be a hard disk or asemiconductor memory. Alternatively, a control program may beappropriately transmitted from another apparatus through, e.g., adedicated line.

Further, by way of example, when the temperatures of the cup CP, the gasexhaust pipe 59 and the liquid drain pipe 57 respectively measured bythe temperature sensors 64, and 67 fall out of preset ranges, thecontroller 30 determines that abnormality has occurred, and controls analarm device 45 to give an alarm based on the abnormality determination.The alarm device 45 may be, but not limited to, a buzzer, an alarm lamp,an alarm mark on a manipulation display, or the like.

Now, a series of processes performed by the above-described coating anddeveloping system 1 will be explained.

First, in the cassette station 10, the wafer transfer device 21 accessesthe wafer cassette CR, in which unprocessed wafers W are accommodated,on the cassette mounting table 20 and takes out one of the unprocessedwafers W from the wafer cassette CR. The wafer W taken from the wafercassette CR is then transferred into the alignment unit ALIM, andposition alignment of the wafer W is performed by the alignment unitALIM. Thereafter, by the main wafer transfer mechanism 22, the wafer Wis transferred into the adhesion unit AD for performing ahydrophobicizing process and then is transferred into the cooling unitCOL for performing a cooling process. Afterward, the wafer W istransferred into the resist coating unit COT for performing a resistcoating process; the wafer W is transferred into the prebaking unit PABfor performing a heating process; and then the wafer W is transferredinto the cooling unit COL for performing a cooling process. Thereafter,the wafer W is transferred by the wafer transfer device 24 into thenon-illustrated exposure apparatus via the interface section 12, and anexposure process is performed in the exposure apparatus. After theexposure process of the wafer W is completed, the wafer W is transferredinto the post exposure baking unit PEB for performing a heating processand then is transferred into the cooling unit COL for performing acooling process. Subsequently, the wafer W is transferred into thedeveloping unit DEV, and a developing process is performed by thedeveloping unit DEV. After the developing process is finished, a heatingprocess (post baking) may be performed. Then, the wafer W is transferredinto the cooling unit COL, and a cooling process is performed by thecooling unit COL and the wafer W is then returned back into the wafercassette CR by the extension unit EXT.

FIG. 6 is a diagram schematically illustrating major parts of thedeveloping unit in accordance with the embodiment of the presentdisclosure. Further, in FIG. 6, elaboration of parts already describedin FIGS. 4 and 5 will be omitted.

Further, FIG. 6 schematically illustrates positions of the respectivenozzles when a rinse solution removing process is performed after thecompletion of a developing solution supply process and a rinse solutionsupply process to be described later with reference to FIG. 7. That is,the developing solution nozzle 36 is located outside the cup CP, and therinse nozzle 15 is located at a position slightly deviated from anapproximate center of the wafer W toward a periphery of the wafer W. Thevapor supply nozzle 16 is placed at a position above the approximatecenter of the wafer W.

The vapor supply mechanism 33 includes a vapor generating tank 71 thatgenerates vapor 44 by vaporizing a first processing solution 43including a hydrophobicizing agent. The vapor generating tank 71 storesthe first processing solution 43 therein. The vapor generating tank 71is connected with one end of the supply pipe 33 a for supplying thevapor 44 of the first processing solution. As stated above, the otherend of the supply pipe 33 a is connected with the vapor supply nozzle 16via a valve 72 configured to be opened and closed by the controller 30.

Connected to the vapor generating tank 71 is one end of a carrier gassupply pipe 73 for supplying a carrier gas such as a N₂ gas. The otherend of the carrier gas supply pipe 73 is connected with a carrier gassupply source 75 via a valve 74 configured to be opened and closed bythe controller 30. As the carrier gas supplied into the vapor generatingtank 71 from the carrier gas supply source 75 pressurizes the inside ofthe vapor generating tank 71, the vapor 44 generated in the vaporgenerating tank 71 is supplied into the vapor supply nozzle 16 throughthe supply pipe 33 a. If the first processing solution 43 includesTMSDMA as will be described later, the first processing solution 43 mayreadily react with moisture in the atmosphere. For this reason, by usingthe carrier gas such as the N₂ gas, the first processing solution 43 andthe vapor 44 of the first processing solution may be prevented fromreacting with the moisture in the atmosphere.

Furthermore, on a part of the supply pipe 33 a, the supply pipe 33 a isconnected with one end of a dilution gas supply pipe 76 for supplying adilution gas such as a N₂ gas. The other end of the dilution gas supplypipe 76 is connected with a dilution gas supply source 78 via a valve 77configured to be opened and closed by the controller 30.

In the vapor supply mechanism 33 configured as described above, thevalve 74 is opened under the control of the controller 30, and thecarrier gas is supplied from the carrier gas supply source 75 into thevapor generating tank 71 through the carrier gas supply pipe 73 at acertain flow rate. Then, the valve 72 is opened, and the vapor 44 of thefirst processing solution vaporized within the vapor generating tank 71is supplied into the vapor supply nozzle 16 through the supply pipe 33 aalong with the carrier gas. Here, the vapor 44 of the first processingsolution may be supplied into the vapor supply nozzle 16 after the vapor44 is diluted with the dilution gas introduced into the supply pipe 33 afrom the dilution gas supply source 78 via the valve 77 and the dilutiongas supply pipe 76. On the contrary, in order to stop the supply of thevapor 44 of the first processing solution into the vapor supply nozzle16, the valve 72 of the supply pipe 33 a and the valve 77 of thedilution gas supply pipe 76 are closed, and the valve 74 is also closedto thereby stop the supply of the carrier gas from the carrier gassupply source 75.

In addition, a non-illustrated supply source for continuously supplyingthe first processing solution 43 including the hydrophobicizing agentmay be connected with the vapor generating tank 71 via a non-illustratedsupply pipe. Further, it may also be possible to install anon-illustrated liquid surface sensor that detects a maximum and minimumheight of a surface of the stored first processing solution 43 and sendsa detection signal to the controller 30.

Here, the hydrophobicizing agent that hydrophobicizes the resist patternmay not be particularly limited. By way of example, a molecular compoundhaving a silyl group of (CH₃)₃Si may be used as the hydrophobicizingagent. One example of such a silyl group may be TMSDMA(Trimethylsilyldimethylamine).

Furthermore, in the present embodiment, a mixture of a hydrophobicizingagent and an organic solvent for diluting the hydrophobicizing agent maybe used as the first processing solution instead of the hydrophobicizingagent itself. A fluorine-containing organic solvent for diluting thehydrophobicizing agent may be, but not limited to, a hydrofluoroether(HFE)-based solvent (methylperfluoroisobutylether,methylperfluorobutylether, or a mixture thereof) having highervolatility than pure water. Further, xylene, hexamethyldisilazane or thelike may also be used. The HFE-based solvent does not dissolve a resistand thus can be supplied onto the resist.

Further, the vapor generating tank 71 may include a temperaturecontroller composed of, e.g., a heating device such as a heater or acooling device such as a Peltier element capable of controlling aninternal temperature of the vapor generating tank 71 so as to generatean optimum amount of vapor 44 depending on the hydrophobicizing agentincluded in the first processing solution 43. When TMSDMA or TMSDMAdiluted with HFE is used as the hydrophobicizing agent, the temperaturecontroller may control the internal temperature of the vapor generatingtank 71 to be substantially the same as a room temperature.

Now, referring to FIGS. 7 to 11, a developing method using thedeveloping unit will be described. FIG. 7 is a flowchart for describinga process sequence, and FIGS. 8 to 11A are side views for illustratingrespective processes.

As depicted in FIG. 7, the developing method in accordance with thepresent embodiment may include a developing solution supply process(step S11), a rinse solution supply process (step S12), a film thicknessadjusting process (step S13), a rinse solution removing process (stepsS14 to S16) and a drying process (step S17). The rinse solution removingprocess may include a first removing process (step S14), a secondremoving process (step S15) and a third removing process (step S16).

Furthermore, example processing recipes for the developing method shownin FIG. 7 are specified in Table 1.

TABLE 1 Nozzle position (mm) Rotation with respect Step Time speed tosubstrate Liquid No. Process name (sec) (rpm) center chemical S12 Rinsesolution 2~15 0~1200 0 Rinse supply process solution S13 Film thickness3 1000 — — adjusting process S14 1^(st) removing 3 1000 0 Vapor ofprocess first processing solution S15 2^(nd) removing 3 100 25  Vapor ofprocess first processing solution S16 3^(rd) removing 1 1000 150  Vaporof process first processing solution S17 Drying process 15 2000 — —

From the left of Table 1, columns represent a step number, a processname, time, a rotation speed (rpm), a nozzle position (mm) with respectto a substrate center and a kind of a liquid chemical supplied in eachstep in sequence. Further, the nozzle position (mm) with respect to thesubstrate center indicates a position when a wafer having a diameter ofabout 12 inches is processed.

First, the developing solution supply process (step S11) is performed.In this developing solution supply process (step S11), a developingsolution 41 is supplied onto the wafer W, and a resist pattern 29 isdeveloped.

The spin chuck 52 is elevated upward and receives the wafer W from themain wafer transfer mechanism 22. Then, the spin chuck 51 is lowered,and the wafer W having the resist pattern 29 formed thereon isaccommodated in the cup CP. Thereafter, as illustrated in FIG. 8A, thedeveloping solution nozzle 36 is moved over the wafer W while supplyingthe developing solution 41 onto the wafer W. After the supply of thedeveloping solution 41 is completed, the wafer W is left in that statefor, e.g., about 60 seconds, so that the developing process progresses.Here, in order to achieve high throughput, the developing solution 41may be supplied while the wafer W is being rotated. In such a case, thedeveloping solution 41 may be diffused by rotating the wafer W at apreset rotation speed. Then, the wafer W is maintained in that statefor, e.g., about 60 seconds, so that the developing process progresses.

Subsequently, the rinse solution supply process (step S12) is carriedout. In the rinse solution supply process (step S12), a rinse solution42 is supplied onto the wafer W of which the resist pattern 29 isdeveloped, so that the developing solution 41 is removed from the waferW.

As shown in FIG. 8B, the developing solution nozzle 36 is moved out ofthe cup, and the rinse nozzle 15 is moved to a position above anapproximate center of the wafer W. Then, as illustrated in FIG. 8C, therinse solution 42 is supplied while the wafer W is being rotated, sothat the developing solution 41 is washed away. Here, since the supplyof the rinse solution 42 is performed while the wafer W is beingrotated, the surface of the wafer W can be rinsed by the rinse solution42 while the developing solution 41 is scattered away.

A liquid film (pure water puddle) of the rinse solution (pure water) 42is formed on the surface of the wafer W. In order to prevent a topsurface 29 a of the resist pattern 29 to be described later withreference to FIG. 12 from being exposed out of the rinse solution 42,the rotation speed of the wafer W is set to be relatively low, e.g.,about 0 rpm to about 1200 rpm and, more desirably, about 500 rpm. If thetop surface 29 a of the resist pattern 29 is exposed out of the rinsesolution 42, pattern collapse may be caused due to a surface tension ofthe rinse solution 42. Thus, by rotating the wafer W at a relatively lowspeed of about 0 rpm to about 1200 rpm, a flow velocity of the rinsesolution 42 on the wafer W can be reduced, so that collapse of theresist pattern 29 can be avoided when the developing solution 41 isremoved. Alternatively, the wafer W may be rotated in multiple steps.For example, the wafer W may be rotated at about 100 rpm for about 2seconds, then rotated at about 1200 rpm for about 3 seconds and thenrotated at about 500 rpm for about 10 seconds.

Subsequently, the film thickness adjusting process (step S13) isperformed. In the film thickness adjusting process (step S13), thesupply of the rinse solution 42 is stopped, and a part of the rinsesolution 42 is scattered away by rotating the wafer W, and, thus, athickness of the liquid film of the rinse solution 42 is adjusted.

As depicted in FIG. 8 d, the thickness of the liquid film (pure waterpuddle) of the rinse solution (pure water) 42 is reduced by increasingthe rotation speed of the wafer W. By reducing the thickness of theliquid film (pure water puddle) of the rinse solution (pure water) 42, apart of the rinse solution may be repelled and a part of the surface ofthe wafer W would be exposed when the vapor 44 of the first processingsolution is supplied during the subsequent rinse solution removingprocess (steps S14 to S16). Thus, an interface B between the rinsesolution 42 and an atmosphere (vapor 44 of the first processingsolution) can be formed on the surface of the wafer W. The rotationspeed of the wafer W may be set to be, e.g., about 1000 rpm.

Thereafter, the rinse solution removing process (steps S14 to S16) iscarried out. In the rinse solution removing process (step S14 to stepS16), the wafer W is rotated while the vapor 44 of the first processingsolution is supplied onto the wafer W, so that the rinse solution 42 isscattered (spun) and removed away. Further, the rinse solution removingprocess (step S14 to step S16) includes the first removing process (stepS14), the second removing process (step S15) and the third removingprocess (step S16), as mentioned above.

Below, there will be discussed an example in which the rinse solution 42is scattered and removed by rotating the wafer W while the vapor 44 ofthe first processing solution is being supplied onto the wafer W.However, it may be also possible to rotate the wafer W after the vapor44 of the first processing solution is supplied. In such a case,although the rotation of the wafer W is not performed while the vapor 44of the first processing solution is being supplied, the wafer W may berotated in an atmosphere including the vapor 44 of the first processingsolution, so that the rinse solution 42 is scattered and removed awayfrom the wafer W.

First, the first removing process (step S14) is carried out. In thefirst removing process (step S14), the wafer W is rotated while thevapor 44 of the first processing solution is being supplied onto theapproximate center of the wafer W, so that the rinse solution 42 isscattered and removed away.

As illustrated in FIG. 9A, the rinse nozzle 15 is moved out of the cupCP, and the vapor supply nozzle 16 is moved to a position above theapproximate center of the wafer W. Then, as illustrated in FIG. 9B,while supplying the vapor 44 of the first processing solution from thevapor supply nozzle 16 located at a position above the approximatecenter of the wafer W, the wafer W is rotated by the driving motor 54 ata first rotation speed R1 for a first time T1.

When the vapor supply nozzle 16 is located at the ‘position above theapproximate center of the wafer W’, the position of the vapor supplynozzle 16 may be referred to as a first position P1. By way of example,the first position P1 may be, e.g., about 0 mm to about 5 mm and, moredesirably, about 0 mm.

The first rotation speed R1 may be adjusted so as to reduce thethickness of the liquid film (pure water puddle) of the rinse solution(pure water) 42, as in the film thickness adjusting process (step S13).By way of example, the first rotation speed R1 may be set to be about500 rpm to about 1500 rpm and, more particularly, to about 1000 rpm.

The first time T1 may be substantially the same as a time period takenuntil the interface between the rinse solution 42 and the atmosphere(vapor 44 of the first processing solution) is formed on the surface ofthe wafer W after the supply of the vapor 44 of the first processingsolution is begun, as will be described below. Further, the first timeT1 may be a time period during which the resist pattern 29 is notdissolved. Since the TMSDMA used as the hydrophobicizing agent has aproperty of dissolving the resist, it is necessary that the first timeT1 may be set to be, e.g., about 0.5 to about 5 seconds and, moredesirably, about 3 seconds.

As illustrated in FIG. 9 c, if the vapor 44 of the first processingsolution is supplied and, thus, a concentration, i.e., a pressure of thevapor 44 of the first processing solution increases at the approximatecenter of the wafer W, the rinse solution 42 may be moved to a peripheryof the wafer W in which the concentration, i.e., the pressure of thevapor 44 of the first processing solution is low. As a result, theliquid film of the rinse solution 42 may be recessed at the approximatecenter of the wafer W, so that a thickness of the liquid film at theapproximate center of the wafer W would be reduced, whereas thethickness of the liquid film at the periphery of the wafer W would beincreased. Then, if the vapor 44 of the first processing solutioncontinues to be supplied and the rinse solution 42 is scattered away bythe rotation of the wafer W, a part of the rinse solution 42 may berepelled on the approximate center of the wafer W and be removed away,as illustrated in FIG. 9D. As a consequent, a part of the surface of thewafer W may be exposed, and the interface B between the rinse solution42 and the atmosphere (vapor 44 of the first processing solution) isformed on the surface of the wafer W.

If the concentration of the vapor 44 of the first processing solutionincreases at the approximate center of the wafer W, the vapor 44 of thefirst processing solution and the rinse solution 42 may be mixed witheach other, resulting in reduction of the surface tension of the rinsesolution 42. Furthermore, if the concentration of the vapor of the firstprocessing solution 44 increases at the approximate center of the waferW, the vapor 44 of the first processing solution and the rinse solution42 may be mixed with each other, and the mixture may reach the surfaceof the resist pattern 29 on the wafer W and may hydrophobicize thesurface of the resist pattern 29.

Further, in FIGS. 9B to 10D, the vapor 44 of the first processingsolution supplied from the vapor supply nozzle 17 is shown to have acertain area for the purpose of illustration. Since, however, the vapor44 of the first processing solution diffuses as a gas, there exists noclear boundary.

Subsequently, the second removing process (step S15) is performed. Inthe second removing process (step S15), the rinse solution 42 isscattered away by rotating the wafer W while slightly shifting theposition, where the vapor 44 of the first processing solution issupplied onto the wafer W, toward the periphery of the wafer W from theapproximate center thereof.

As illustrated in FIG. 10A, while the position of the vapor supplynozzle 16 with respect to the approximate center of the wafer W is beingshifted to a position slightly deviated toward the periphery of thewafer W from the approximate center of the wafer W by the motor 19 for asecond time T2, the wafer W is rotated at a second rotation speed R2 bythe driving motor 54.

When the vapor supply nozzle 16 is located at the ‘position slightlydeviated toward the periphery of the wafer W’ from the center of thewafer W, the position of the vapor supply nozzle 16 may be referred toas a second position P2. By way of example, the second position P2 maybe, e.g., about 5 mm to about 50 mm and, more desirably, about 25 mm.

The second rotation speed R2 may be adjusted to reduce a speed formoving the interface B between the rinse solution 42 and the atmosphere(vapor 44 of the first processing solution) toward the periphery of thewafer W, as will be described later. Desirably, the second rotationspeed R2 may be lower than the first rotation speed R1, and the secondrotation speed R2 may be set to be about 0 rpm to about 500 rpm and,more desirably, about 100 rpm.

The second time T2 may be substantially the same as a time period takenuntil the interface B between the rinse solution 42 and the atmosphere(vapor 44 of the first processing solution) starts to be moved instantlytoward the periphery of the wafer W after the interface B is formed, aswill be described below. Further, the second time T2 may be a timeperiod during which the resist pattern 29 is not dissolved. By way ofexample, the second time T2 may be set to be, e.g., about 0.5 to about10 seconds and, more desirably, about 3 seconds.

In the first removing process (step S14), as a part of the rinsesolution 42 is repelled on the approximate center of the wafer W, a partof the surface of the wafer W may be exposed, and the interface Bbetween the rinse solution 42 and the atmosphere (vapor 44 of the firstprocessing solution) may be formed on the surface of the wafer W. Inthis state, if the wafer W is rotated at the same speed, the rinsesolution 42 may be scattered away, so that the interface B between therinse solution 42 and the atmosphere (vapor 44 of the first processingsolution) may be moved toward the periphery of the wafer W instantly.If, however, the interface B between the rinse solution 42 and theatmosphere (vapor 44 of the first processing solution) is moved towardthe periphery of the wafer W too fast, the surface tension of the rinsesolution 42 may not be reduced, or the surface of the resist pattern 29may not be hydrophobicized by the vapor 44 of the first processingsolution, resulting in collapse of the resist pattern 29. Accordingly,in the second removing process (step S15), by shifting the position forsupplying the vapor 44 of the first processing solution slightly towardthe periphery of the wafer W from the approximate center thereof, thesurface tension of the rinse solution 42 may be reduced at the peripheryof the wafer W or the surface of the resist pattern 29 may behydrophobicized thereat. Further, by decreasing the rotation speed ofthe wafer W, the speed at which the interface B between the rinsesolution 42 and the atmosphere (vapor 44 of the first processingsolution) is moved toward the periphery of the wafer W can also bedecreased. Then, instant shift of the interface B between the rinsesolution 42 and the atmosphere (vapor 44 of the first processingsolution) toward the periphery of the wafer W is awaited.

In accordance with the first embodiment, in the first removing process(step S14), the vapor supply nozzle 16 is shifted toward the peripheryof the wafer W as illustrated in FIG. 10A after the interface B betweenthe rinse solution and the atmosphere (vapor 44 of the first processingsolution) is formed on the approximate center of the wafer W as depictedin FIG. 9D. However, the shift of the vapor supply nozzle 16 may bestarted at the same time or slightly before the interface B between therinse solution 42 and the atmosphere (vapor 44 of the first processingsolution) is formed on the approximate center of the wafer W. In such acase, in the first removing process (step S14), the rinse solution 42may be scattered away by rotating the wafer W while supplying the vapor44 of the first processing solution onto the approximate center of thewafer W in a state that the surface of the approximate center of thewafer W is yet to be completely dried. Furthermore, in the secondremoving process (step S15), in a state that the surface of theapproximate center of the wafer W is yet to be completely dried, therinse solution 42 may be scattered away by rotating the wafer W whileslightly shifting the position for supplying the vapor 44 of the firstprocessing solution toward the periphery of the wafer W from theapproximate center thereof. In such a case, this state is not exactlythe same as the state shown in FIG. 9D.

Subsequently, the third removing process (step S16) is performed. In thethird removing process (step S16), the rinse solution 42 is scatteredand removed by rotating the wafer W while instantly shifting theposition where the vapor 44 of the first processing solution is suppliedto an approximate edge of the wafer W.

As illustrated in FIGS. 10A to 10D, while the position of the vaporsupply nozzle 16 with respect to the center of the wafer W is instantlyshifted to the approximate edge of the wafer W for a third time T3 bythe motor 19, the wafer W is rotated at a third rotation speed R3 by thedriving motor 54.

When the vapor supply nozzle 16 is located at ‘the approximate edge ofthe wafer W’, the position of the vapor supply nozzle 16 may be referredto as a third position P3. By way of example, the third position P3 maybe set to be about 100 mm to about 200 mm and, more particularly, about150 mm.

The third rotation speed R3 may be adjusted so as to allow the interfaceB between the rinse solution 42 and the atmosphere (vapor 44 of thefirst processing solution) to be instantly moved to the approximate edgeof the wafer W, as will be described later. Desirably, the thirdrotation speed R may be higher than the second rotation speed R2. By wayof example, the third rotation speed R3 may be in the range of about 500rpm to about 1500 rpm and, more desirably, the third rotation speed R3may be about 1000 rpm.

The third time T3 may be substantially the same as a time period takenuntil the interface B between the rinse solution 42 and the atmosphere(vapor 44 of the first processing solution) is instantly moved to theapproximate edge of the wafer W from the approximate center of the waferW, as will be described below. Further, the third time T3 may be a timeperiod during which the resist pattern 29 is not dissolved. By way ofexample, the third time T3 may be set to be, e.g., about 1 second toabout 10 seconds and, more desirably, about 1 second.

By increasing the rotation speed of the wafer W, the interface B betweenthe rinse solution 42 and the atmosphere (vapor 44 of the firstprocessing solution) is instantly moved to the periphery of the wafer W.Further, by instantly moving the vapor supply nozzle 16 to theapproximate edge of the wafer W, the position where the vapor 44 of thefirst processing solution is supplied to the wafer W can be moved alongwith the interface B between the rinse solution 42 and the atmosphere(vapor 44 of the first processing solution). That is, by rotating thespin chuck 52 by the driving motor 54 while moving the position, wherethe vapor 44 of the first processing solution is supplied, at a speedcorresponding to a speed at which the rinse solution 42 is scattered andmoved by the motor 19, the rinse solution 42 can be scattered (spun) andremoved.

Further, in the first embodiment, the rinse solution removing process isdescribed to include steps S14 to S16. However, the rinse solution 42may be removed by performing only step S14 without performing steps S15and S16. That is, the rinse solution 42 may be scattered and removed byrotating the wafer W while supplying the vapor 44 of the firstprocessing solution to the approximate center of the wafer W withoutmoving the vapor supply nozzle 16 from the approximate center of thewafer W.

Then, the drying process (step S17) is performed. In the drying process(step S17), the wafer W is rotated at a preset rotation speed and thusis dried.

As illustrated in FIG. 11, the wafer W is rotated by the driving motor54 at a high rotation speed of, e.g., about 1500 rpm to about 2500 rpm,more desirably, about 2000 rpm, so that the surface of the wafer W issufficiently dried.

Furthermore, in the first embodiment, the rinse solution 42 may not besupplied again for cleaning after the rinse solution removing process(steps S14 to S16). However, depending on conditions such as the kind ofthe resist or the rinse solution 42, the shape of the resist pattern 29on the wafer W, and the like, a rinse solution supply process may beperformed again between the rinse solution removing process and thedrying process (step S17). In such a case, since the surface of theresist pattern 29 is already hydrophobicized as a result of performingthe rinse solution removing process (steps S14 to S16), the resistpattern 29 may not collapse even if the rinse solution supply process isperformed again.

Below, an effect of preventing collapse of a resist pattern by using thevapor of the first processing solution and an effect of reducing anamount of usage of the first processing solution in accordance with thefirst embodiment will be discussed. Further, in the followingdescription, a resist pattern may be simply referred to as a ‘pattern’.

FIG. 12 provides a diagram for describing a relationship between acontact angle of a rinse solution and a force for collapsing patternswhen the rinse solution exists between the patterns. In the course ofdrying the rinse solution 42 after rinsing a gap between two resistpatterns 29 by the rinse solution 42, one side of the resist pattern 29may be in contact with the rinse solution 42 while the other sidethereof is dried and is in contact with air, as depicted in FIG. 12. Insuch a state, since the one side of the resist pattern 29 is pressed bythe rinse solution 42 while the other side is pressed by the air, aforce for collapsing the resist patterns 29 may be exerted due to such apressure difference. The force F for collapsing the patterns may berepresented by the following Eq. (1).

$\begin{matrix}{\left\lbrack {{Eq}.\mspace{14mu} 1} \right\rbrack \mspace{675mu}} & \; \\{F = {\frac{2\gamma \; \cos \; \theta}{D}{HL}}} & (1)\end{matrix}$

Here, γ is a surface tension of the rinse solution; θ, a contact angleof the rinse solution with respect to a pattern; D, a distance betweenpatterns; H, a height of the pattern; and L, a length of the pattern.The force F for collapsing the pattern generates a moment for bendingthe pattern. If the width of the pattern is W1, a maximum stress σ_(MAX)applied to the pattern may be represented by the following Eq. (2).

$\begin{matrix}{\left\lbrack {{Eq}.\mspace{14mu} 2} \right\rbrack \mspace{675mu}} & \; \\{\sigma_{MAX} = {\frac{6\gamma \; \cos \; \theta}{D}\left( \frac{H}{W\; 1} \right)^{2}}} & (2)\end{matrix}$

Accordingly, when σ_(MAX) exceeds a collapse stress σ_(CRT)(σ_(MAX)>σ_(CRT)) of the pattern, the pattern may be collapsed. Based onthese equations, some methods to prevent collapse of the pattern may beconsidered: (1) enlarging the distance D between patterns; (2) reducingan aspect ratio of the pattern by decreasing the height H of the patternor by increasing the width W1 of the pattern; (3) reducing the surfacetension γ of the rinse solution 42; and (4) reducing cos θ by increasingthe contact angle θ of the rinse solution 42 with respect to thepattern.

Among the mentioned methods, in the developing method in accordance withthe first embodiment, the maximum stress σ_(MAX) applied to the patternmay be reduced to prevent the pattern collapse by (3) decreasing thesurface tension γ of the rinse solution 42 or by (4) increasing thecontact angle θ.

FIG. 13 is a diagram for describing a reaction mechanism of ahydrophobicizing process for hydrophobicizing a surface of a resistpattern by a first processing solution including TMSDMA. TMSDMA includedin the processing solution may have a silyl group of (CH₃)₃Si in itsmolecule. Meanwhile, resist has an OH group in its polymer structure.The silyl group of the TMSDMA is substituted with H of the OH group ofthe resist on the surface of the resist pattern. The OH group ishydrophilic, whereas a group formed by substituting the H of the OHgroup with the silyl group is hydrophobic. Accordingly, the surface ofthe resist pattern may be hydrophobicized by the hydrophobic groupformed on the surface of the resist pattern.

The contact angle θ of the rinse solution 42 with respect to the resistpattern 29 shown in FIG. 12 was measured after the completion of therinse solution removing process for removing the rinse solution 42 whilesupplying the vapor 44 of the first processing solution, and the contactangle θ was found to range from about 85° to about 95°. Accordingly,when the rinse solution 42 is removed from between the patterns, patterncollapse may not be caused. Furthermore, once the contact angle θ of therinse solution 42 with respect to the resist pattern 29 is increased,i.e., after the hydrophobicization of the surface of the resist pattern29 is performed, such a large contact angle can also be achieved for therinse solution 42 composed of pure water.

In the present embodiment, a first processing solution composed ofTMSDMA diluted with HFE may be used instead of TMSDMA. Even if theTMSDMA is diluted with HFE, it is also possible to achieve the effect ofhydrophobicizing the surface of the resist pattern by the silyl group inthe TMSDMA. Meanwhile, since the HFE has fluorine, the surface of theresist pattern 29 may be coated with fluorine. Accordingly, even in casethe first processing solution composed of the TMSDMA diluted with theHFE is used, a contact angle in the above-specified high angular rangecan also be obtained.

Further, a hydrophobic group is formed on the surface of the resistpattern 29 by the silyl group of the TMSDMA, so that the surface of theresist pattern 29 is hydrophobicized. By way of example, after thehydrophobic group is formed, an additional reaction may be made byperforming heat treatment such as post baking, and, thus, the surface ofthe resist pattern 29 may be chemically stabilized, as in the case ofso-called silylation. Accordingly, since the surface of the resistpattern 29 has resistance against etchant used in a subsequent processof etching the wafer W by using the resist pattern 29 as a mask,selectivity, i.e., a ratio of an etching rate of the wafer W to anetching rate of the resist pattern 29 can be improved, and formation offiner patterns or formation of patterns having a higher aspect ratio canbe carried out accurately.

Now, investigation result of a pattern collapse preventing effect by thedeveloping method in accordance with the first embodiment will bedescribed with reference to Table 2.

Experimental Example 1

In an experimental example 1, as for wafers on which resist was coatedand pattern exposure was performed while varying a dose amount duringthe exposure in the range of about 27 mJ to about 32 mJ, development ofresist patterns formed on the wafers was carried out by performing stepsS11 to S17 as described in FIG. 7. Each of steps S13 to S17 wasperformed according to example processing recipes specified in Table 1.In steps S14 to S16, a vapor of a first processing solution made of 100%of TMSDMA was used. The resist pattern was formed to have a line widthof about 120 nm, a space width of about 120 nm (a pitch of about 240 nm)and a height of about 380 nm. Then, by using a SEM (Scanning ElectronMicroscope), it was observed whether collapse of pattern had occurred inthe patterns formed by using the respective dose amounts. The result isdepicted in Table 2.

Comparative Example 1

In a comparative example 1, as for wafers on which the same patternexposure as in the experiment example 1 was performed, development ofresist patterns having the same shapes as those in the experimentalexample was conducted by performing steps S11 to S13 and step S17 inFIG. 7 while omitting steps S14 to S16. In this example, however, arinse solution composed of HFE was used in step S13 instead of usingpure water. Further, as in the experimental example 1, it was observedwhether collapse of pattern had occurred in the patterns formed by usingrespective dose amounts. The result is depicted in Table 2.

Comparative Example 2

In a comparative example 2, as for wafers on which the same patternexposure as in the experiment example 1 was performed, development ofresist patterns having the same shapes as those in the experimentalexample was conducted by performing steps S11 to S13 and step S17 inFIG. 7 while omitting steps S14 to S16. The comparative example 2corresponds to a conventional developing process in which rinse isperformed by using pure water. Further, as in the experimental example1, it was observed whether collapse of pattern had occurred in thepatterns formed by using respective dose amounts. The result is depictedin Table 2.

TABLE 2 Dose amount (mJ) during exposure Example 27 28 29 30 31 32Experimental example 1 ◯ ◯ ◯ ◯ ◯ ◯ (Removing rinse solution inatmosphere of vapor of TMSDMA) Comparative example 1 ◯ ◯ X ◯ X X(Removing rinse solution after substituting the rinse solution with HFE)Comparative example 2 ◯ ◯ X X X X (Removing rinse solution (pure water))(◯: no pattern collapse has occurred, X: pattern collapse has occurred)

In Table 2, ◯ indicates that pattern collapse has not occurred under thecorresponding condition, while x indicates that pattern collapse hasoccurred under the corresponding condition.

As shown in the results of Table 2, no pattern collapse has occurredunder all conditions in the experimental example 1. Meanwhile, in thecomparative examples 1 and 2, pattern collapse has occurred under somespecific conditions. Thus, it is clear that pattern collapse can be moreeffectively suppressed in the experimental example 1 than in thecomparative examples 1 and 2. It is because a maximum stress σ_(MAX)applied to the pattern is reduced by substituting H of an OH group onthe surface of a resist pattern with a silyl group of the TMSDMA so asto improve hydrophobic property and increasing a contact angle θ of therinse solution with respect to the pattern.

Furthermore, in the first embodiment, since the vapor of the firstprocessing solution is supplied, the amount of usage of the firstprocessing solution can be reduced as compared to a case of directlysupplying the first processing solution itself. By way of example, inthe present embodiment, the amount of the first processing solution usedfor processing one sheet of wafer may be about 2.5 μl. On the contrary,if the first processing solution in a liquid phase is supplied, not avapor, the amount of the first processing solution for processing onesheet of wafer may be about 100 μl in order to obtain the same effect.Accordingly, in accordance with the present embodiment, the amount ofusage of the hydrophobicizing agent can be reduced to about 1/40, sothat cost for substrate processing can be reduced greatly.

The first embodiment has been described for the case of applying thesubstrate processing apparatus in accordance with the present disclosureto the developing apparatus and applying the substrate processing methodin accordance with the present disclosure to the developing method.However, application of the substrate processing apparatus in accordancewith the present disclosure may not be limited to the developingapparatus that performs a developing process on the substrate. By way ofexample, the substrate processing apparatus in accordance with thepresent disclosure may be also applicable to a single-substrate typecleaning apparatus that performs a cleaning process on a singlesubstrate held on a spin chuck. When applying the substrate processingapparatus in accordance with the present disclosure to the cleaningapparatus, it may be possible to use an apparatus having the sameconfiguration as that of the developing apparatus illustrated in FIGS. 4and 5 excepting that it does not have the developing solution supplymechanism. Further, when applying the substrate processing method inaccordance with the present disclosure to the cleaning method, thedeveloping method described in FIG. 7 may be used while omitting thedeveloping solution supply process.

First Modification Example of the First Embodiment

Now, referring to FIG. 14 and FIGS. 15A to 15E, a developing apparatusand a developing method in accordance with a first modification exampleof the first embodiment will be explained.

The developing apparatus in accordance with the first modificationexample is different from the developing apparatus in accordance withthe first embodiment in that a rinse solution is removed while detectinga moving position of an interface between the rinse solution and anatmosphere when the rinse solution is scattered in the atmosphereincluding the vapor of the first processing solution.

FIG. 14 is a cross sectional view illustrating a developing unit inaccordance with the first modification example. FIGS. 15A to 15E areschematic diagrams illustrating a principle of a method for detectingthe position of the interface between the rinse solution and theatmosphere. In the following description (including description of theother modification examples and other embodiments below), the same partsas described above will be assigned same reference numerals, andelaboration thereof will be omitted. Further, in FIG. 14, illustrationof a processing chamber is omitted.

In this modification example, units other than a developing unit DEV ofa coating and developing system including the developing apparatus maybe the same as those described in the first embodiment with reference toFIGS. 1 to 3.

Meanwhile, in this first modification example, there is provided adetecting unit 80 for detecting whether or not an interface B between arinse solution 42 and an atmosphere (vapor 44 of a first processingsolution) is formed when a part of the rinse solution is repelled andremoved and a part of the surface of a wafer W is exposed on anapproximate center of the wafer W.

Alternatively, the detecting unit 80 may detect a position of theinterface B between the rinse solution 42 and the atmosphere (vapor 44of the first processing solution) in order to shift a position, wherethe vapor 44 of the first processing solution is supplied onto the waferW, at a speed corresponding to a speed at which the rinse solution 42 isscattered and moved.

As depicted in FIG. 14, the detecting unit 80 irradiates a laser beam Lto the wafer W, held on a spin chuck 52, on which the rinse solution 42has been supplied, and detects an amount of reflection light reflectedfrom a surface of the wafer W. The detecting unit 80 includes aretro-reflective laser sensor (laser generating unit) 81, a reflectingplate 82 and a laser receiving unit 83. The laser generating unit 81irradiates light of the laser beam L onto the surface of the wafer W,and the reflecting plate reflects the laser beam L irradiated to andreflected from the surface of the wafer W. The laser receiving unit 83receives the reflected light of the laser beam L that is reflected bythe reflecting plate 82 and reflected again on the surface of the waferW. Further, although attenuation of the laser beam may vary depending onthe kind of the wafer W, the attenuation of the laser beam can bereduced by minimizing a reflection angle.

Further, in the present modification example, the laser beam is used asthe irradiation light irradiated to the wafer W. However, theirradiation light may not be limited to the laser beam, but it may be ofany kind as long as it has some degree of straightforwardness. Here,instead of the retro-reflective laser sensor 81 and the laser receivingunit 83, a light generating unit and a light receiving unitcorresponding to the irradiation light may be used.

The detecting unit 80 is connected with a detecting board 85 via anamplifier 84 so as to convert a detected analog signal into a digitalsignal for detection.

The detecting board 85 includes a CPU 86. The CPU 86 measures analogsignals outputted from the detecting unit 80 and performs an operationfor comparing a value obtained when the surface of the wafer W iscovered with the rinse solution immediately before the interface B isformed and a value obtained when the interface B is formed and thesurface of the wafer W is thus exposed. Alternatively, the CPU 86 mayperform an operation for comparing any one of the analog signals with apreset threshold value. Further, the detecting board 85 is connectedwith a computer 88 that outputs a value of the detecting unit 80 and adetermination result on a display 87 based on a signal from the CPU 86.

Further, the CPU 86 controls the motor 19 to rotate and move the vaporsupply nozzle 16, so that the vapor supply nozzle 16 is rotated andmoved, and the CPU 86 detects a position of the vapor supply nozzle 16by detecting a rotation position of the motor 19.

Further, the detecting board 85, the CPU 86, the display 87 and thecomputer 88 and the like may be included in the controller 30.

Now, a developing method in accordance with the first modificationexample will be explained. The developing method in accordance with thepresent modification example is substantially the same as the developingmethod described in the first embodiment with reference to FIG. 7excepting that the developing method in accordance with the firstmodification example is performed while the detecting unit 80 detectswhether or not the interface B between the rinse solution 42 and theatmosphere (vapor 44 of the first processing solution) is formed. In thefollowing, a principle of the method for detecting the position of theinterface B between the rinse solution 42 and the atmosphere (vapor 44of the first processing solution) will be described with reference toFIGS. 15A to 15E.

Before a developing solution supply process (step S11) is performed, thedetecting unit 80 detects a received light amount (level 0) in anOFF-state while a wafer W is held on the spin chuck 52 in order to set athreshold value for noise margin that may be different depending on thekind of a wafer W (see FIG. 15A). Thereafter, when the developingsolution supply process (step S11) is performed, the detecting unit 80is operated at the moment a supply signal for a developing solutionnozzle 36 is turned ON, and the detecting unit 80 measures (detects) areflection amount of a laser beam L irradiated to a surface of the waferW immediately before the supply of a developing solution 41 from thedeveloping solution nozzle 36 is begun (see FIG. 15B). A measured analogsignal is sent to the CPU 82 and the reflection light amount is comparedwith the received light amount of level 0, and the threshold value fornoise margin is set based on a difference between them. Here, thethreshold value for noise margin is set by measuring (detecting) thereflection amount of the laser beam L irradiated to the surface of thewafer W immediately before the developing solution 41 is supplied fromthe developing solution nozzle 36. However, the timing for measuring thereflection light amount may not be limited to immediately before thesupply of the developing solution 41 from the developing solution nozzle36 is started. That is, the reflection amount of the laser beam Lirradiated to the surface of the wafer W may be measured (detected) atany point in time before the developing solution 41 is supplied from thedeveloping solution nozzle 36, and the threshold value for noise margincan be set based on the detected reflection light amount.

Subsequently, a rinse solution supply process (step S12) and a filmthickness adjusting process (step S13) are performed. A laser reflectionamount is measured (detected) after a liquid film thickness of a rinsesolution 42 on the surface of the wafer W is adjusted through the filmthickness adjusting process (step S13). In this state, since the laserbeam L is blocked by the rinse solution 42 and reflectivity decreasesbecause of the rinse solution 42 staying on the wafer W, the reflectionlight amount may be almost level 0 (see FIG. 15C).

Thereafter, a rinse solution removing process (steps S14 to S16) isperformed. While supplying the vapor 44 of the first processing solutionfrom a vapor supply nozzle 16, the wafer W is rotated by a driving motor54, so that the rinse solution 42 is scattered and removed away. In afirst removing process (step S14), the wafer W is rotated whilesupplying the vapor 44 of the first processing solution onto anapproximate center of the wafer W. As a consequence, the rinse solution42 may be scattered and removed from the approximate center of the waferW, and the surface of the wafer W may be exposed, resulting inimprovement of reflectivity. Therefore, a high level of reflection lightamount is detected (see FIG. 15D).

In other words, if a high level of reflection light amount is detected,it may be determined that the rinse solution 42 is scattered and removedon the approximate center of the wafer W. Accordingly, when the highlevel of reflection light amount is detected, a second removing process(step S15) may be started. That is, the rinse solution 42 may be removedwhile shifting a position, where the vapor 44 of the first processingsolution is supplied to the wafer W, toward a periphery of the wafer Wfrom the center of the wafer W based on the detected reflection lightamount.

Then, after a drying process (step S17) is performed and the rinsesolution 42 is removed from the surface of the wafer W, the detectingunit 80 is turned OFF (see FIG. 15E).

By using the detecting unit 80 as described above, it can be detectedwhether the rinse solution 42 exists on the surface of the approximatecenter of the wafer W. Accordingly, the first removing process (stepS14) can be finished and the second removing process (step S15) can bestarted according to the time when the interface B between the rinsesolution 42 and the atmosphere (vapor 44 of the first processingsolution) is formed on the approximate center of the wafer W. Thus, theposition where the vapor 44 of the first processing solution is suppliedcan be moved according to the position on which the rinse solution 42 isscattered and moved. As a result, pattern collapse can be more securelysuppressed when the rinse solution 42 is removed.

Further, in this first modification example, a multiple number of thedetecting units may be installed from the approximate center of thewafer W to the periphery of the wafer W so as to detect presence orabsence of the rinse solution 42 at multiple positions on the wafer W.Alternatively, by rotating (moving) the laser generating unit 81 and thereflecting plate 82 synchronously so as to allow angles formed betweenthe laser beam and the surface of the wafer W to be variedsynchronously, presence or absence of the rinse solution 42 may bedetected at multiple positions on the wafer W. In such a case, bydetecting presence or absence of the rinse solution 42 at the multiplepositions on the wafer W at the respective time, a speed at which therinse solution 42 is scattered and moved on the wafer W can becalculated. Accordingly, the vapor supply nozzle 16 can be moved at aspeed corresponding to a speed at which the interface B between therinse solution 42 and the atmosphere (vapor 44 of the first processingsolution) is moved. Thus, by way of example, the vapor supply nozzle 16can be moved at the same speed as the speed at which the interface Bbetween the rinse solution 42 and the atmosphere (vapor 44 of the firstprocessing solution) is moved in the third removing process (step S16).That is, the rinse solution 42 may be removed while shifting theposition where the vapor 44 of the first processing solution is suppliedto the wafer W at the speed corresponding to the speed at which therinse solution 42 is scattered and moved, based on the detectedreflection light amount.

In this first modification example, a surface of a resist pattern may behydrophobicized by the vapor of the first processing solution includinga hydrophobicizing agent. Accordingly, pattern collapse can besuppressed when the rinse solution is supplied onto a substrate on whichfine resist patterns are formed and then the rinse solution is removedfrom the substrate. Furthermore, by reducing an amount of usage of thehydrophobicizing agent, cost for substrate processing can be reduced.

Further, in accordance with the first modification example, the movingposition of the interface between the rinse solution and the atmospherecan be accurately detected by the detecting unit, and the vapor supplynozzle can be moved to follow up the movement of the interface betweenthe rinse solution and the atmosphere. Accordingly, the vapor of thefirst processing solution can be successfully supplied to the vicinityof the interface between the rinse solution and the atmosphere when theinterface is moved. Thus, pattern collapse can be suppressed moreeffectively. Further, by further reducing an amount of usage of thehydrophobicizing agent, cost for substrate processing can be reduced.

Moreover, in the present modification example, although it has beendescribed that the present disclosure is applied to the developingapparatus, the present disclosure may not be limited to the developingapparatus but can be applied to a single-wafer cleaning apparatus thatperforms a cleaning process on a substrate held on a spin chuck.Furthermore, in the present modification example, although it has beendescribed that the present disclosure is applied to the developingmethod, the present disclosure may not be limited to the developingmethod but can be applied to a single-wafer cleaning method forperforming a cleaning process on a substrate held on a spin chuck.

Second Modification Example of the First Embodiment

Now, referring to FIGS. 16 and 17, a developing apparatus and adeveloping method in accordance with a second modification example ofthe first embodiment will be described.

The developing apparatus in accordance with the second modificationexample is different from the developing apparatus in accordance withthe first embodiment in that a processing solution supply nozzle isprovided to a vapor supply nozzle.

FIG. 16 is a diagram schematically illustrating major parts of adeveloping unit in accordance with the second modification example.

In this second modification example, units other than a developing unitDEV of a coating and developing system including the developingapparatus may be the same as those described in the first embodimentwith reference to FIGS. 1 to 3. Further, the developing unit DEV inaccordance with the second modification example may have the sameconfiguration as that of the developing unit DEV of the coating anddeveloping system in accordance with the first embodiment excepting theprocessing solution supply nozzle. Thus, elaboration of parts in FIG. 16already described in the first embodiment with reference to FIGS. 4 and5 will be omitted.

FIG. 16 schematically illustrates nozzle positions when a rinse solutionremoving process is performed after a developing solution supply processto a film thickness adjusting process are performed as will be describedbelow with reference to FIG. 17. That is, a developing solution nozzle36 is located outside a cup CP; a rinse nozzle 15 is located at aposition slightly deviated toward a periphery of a wafer W from anapproximate center of a wafer W; and a vapor supply nozzle 16 is placedat position above the approximate center of the wafer W.

In the second modification example, a processing solution nozzle 16 a isprovided next to the vapor supply nozzle 16. The processing solutionnozzle 16 a, held by a non-illustrated nozzle holder, is fixed at aleading end of a non-illustrated nozzle scan arm. The processingsolution nozzle 16 a supplies a second processing solution 42 a having asmaller surface tension than that of the rinse solution 42 on a surfaceof the wafer W. As in the case of the vapor supply nozzle 16, thisnozzle scan arm may be rotatable about a non-illustrated motor in a θdirection by the motor. The second processing solution 42 a is suppliedinto the processing solution nozzle 16 a from a non-illustrated secondprocessing solution supply mechanism through a non-illustrated supplypipe. Alternatively, the processing solution nozzle 16 a may be fixed ata leading end of the nozzle scan arm 18 together with the vapor supplynozzle 16.

By way of example, the aforementioned HFE-based solvent having a smallersurface tension than that of the rinse solution 42 such as pure watermay be used as the second processing solution 42 a. Further, xylene,hexamethyldisilazane (HMDS) or the like may also be used.

Moreover, the processing solution nozzle 16 a serves as a secondprocessing solution supply unit in the present disclosure.

Now, a developing method in accordance with the second modificationexample will be discussed with reference to FIG. 17. FIG. 17 is aflowchart for describing a process sequence.

As depicted in FIG. 17, the developing method in accordance with thesecond modification example may include a developing solution supplyprocess (step S21), a rinse solution supply process (step S22), a secondprocessing solution supply process (step S23), a film thicknessadjusting process (step S24), a rinse solution removing process (stepsS25 to S27) and a drying process (step S28). The rinse solution removingprocess may include a first removing process (step S25), a secondremoving process (step S26) and a third removing process (step S27).

First, the developing solution supply process (step S21) and the rinsesolution supply process (step S22) are performed. The developingsolution supply process (step S21) and the rinse solution supply process(step S22) may be carried out in the same ways as steps S11 and S12 inthe first embodiment, respectively.

Then, the second processing solution supply process (step S23) isperformed. In the second processing solution supply process (step S23),the second processing solution 42 a is supplied onto the wafer W onwhich the rinse solution 42 has been already supplied.

The developing solution nozzle 36 is moved out of the cup CP, and theprocessing solution nozzle 16 a is moved to a position above theapproximate center of the wafer W. Then, the second processing solution42 a is supplied while the wafer W is being rotated. Since the supply ofthe second processing solution 42 a is carried out while rotating thewafer W, the surface of the wafer W may be rinsed by the rinse solution42 including the second processing solution 42 a.

By way of example, a liquid film of the rinse solution 42 including thesecond processing solution 42 a is formed on the surface of the wafer W,and a rotation speed of the wafer W may be set to be relatively low,e.g., about 0 rpm to about 1200 rpm, and more desirably, about 500 rpmso as not to allow a top surface of a developed resist pattern to beexposed out of the rinse solution 42. By rotating the wafer W at therelatively low speed of about 0 rpm to about 1200 rpm, a flow velocityof the rinse solution 42 including the second processing solution 42 aon the wafer W can be reduced, thus preventing collapse of a resistpattern 29 when the rinse solution 42 including the second processingsolution 42 a is flown.

Further, in the second processing solution supply process (step S23), alarge amount of second processing solution 42 a may be supplied so as tosubstantially substitute the rinse solution 42 with the secondprocessing solution 42 a. On the contrary, in the second processingsolution supply process (step S23), the second processing solution 42 amay be just dripped on the wafer W on which the rinse solution 42 hasbeen supplied. When dripping the second processing solution 42 on thewafer W, the second processing solution supply process (step S23) maynot be performed prior to the rinse solution removing process, but itmay be performed concurrently with the rinse solution removing process.That is, the rinse solution removing process (steps 25 to 27) may beperformed while dripping the second processing solution 42 a from theprocessing solution nozzle 16 a without performing step S23.

Subsequently, the film thickness adjusting process (step S24) is carriedout. The film thickness adjusting process (step S24) may besubstantially the same as the film thickness adjusting process (stepS13) in accordance with the first embodiment. In this film thicknessadjusting process (step S24), the supply of the second processingsolution 42 a is stopped, and a part of the rinse solution 42 includingthe second processing solution 42 a is scattered away by rotating thewafer W, and, thus, a thickness of the liquid film of the rinse solution42 is adjusted.

Thereafter, the rinse solution removing process (steps 25 to 27) isperformed. In the rinse solution removing process (steps 25 to 27), thewafer W is rotated while vapor 44 of a first processing solution issupplied onto the wafer W, so that the rinse solution 42 including thesecond processing solution 42 a is scattered (spun) and removed away, asin the rinse solution removing process (steps S14 to S16) in accordancewith the first embodiment.

Then, the drying process (step S28) is performed. In the drying process(step S28), the wafer W is dried by being rotated at a preset rotationalspeed, as in the drying process (step S17) in the first embodiment.

In the second modification example, the surface of the resist patternmay be hydrophobicized by the vapor of the first processing solutionincluding a hydrophobicizing agent. Accordingly, pattern collapse can besuppressed when the rinse solution is supplied onto a substrate on whichfine resist patterns are formed and then the rinse solution is removedfrom the substrate. Furthermore, by reducing an amount of usage of thehydrophobicizing agent, cost for substrate processing can be reduced.

In this second modification example, the second processing solutionhaving a smaller surface tension than that of the rinse solution issupplied, and in the rinse solution removing process, the rinse solutionincluding the second processing solution is scattered and removed byrotating the wafer W while supplying the vapor of the first processingsolution including the hydrophobicizing agent. The rinse solutionincluding the second processing solution has a smaller surface tensionthan that of the rinse solution. Accordingly, when the rinse solution issupplied onto the substrate on which fine resist patterns are formed andwhen the rinse solution is removed from this substrate, pattern collapsecan be suppressed more securely.

Furthermore, HFE has a larger specific gravity than that of pure water.Accordingly, when HFE is used as the second processing solution, thesecond processing solution may be positioned under the rinse solutionafter the second processing solution supply process (step S23), therebyallowing the rinse solution to easily escape from the resist pattern.Thus, the effect of preventing pattern collapse can be further improved.

Moreover, in the present modification example, although it has beendescribed that the present disclosure is applied to the developingapparatus, the present disclosure may not be limited to the developingapparatus but can be applied to a single-wafer cleaning apparatus thatperforms a cleaning process on a substrate held on a spin chuck.Furthermore, in the present modification example, although it has beendescribed that the present disclosure is applied to the developingmethod, the present disclosure may not be limited to the developingmethod but can be applied to a single-wafer cleaning method forperforming a cleaning process on a substrate held on a spin chuck.

Second Embodiment

Now, a developing apparatus and a developing method in accordance with asecond embodiment of the present disclosure will be described withreference to FIGS. 18 to 22B.

The developing apparatus in accordance with the second embodiment isdifferent from the developing apparatus in accordance with the firstembodiment in that a rinse solution is scattered while a position wherevapor of a first processing solution is supplied by a vapor supplynozzle is being shifted from a periphery of a wafer toward a center ofthe wafer.

FIG. 18 is a diagram schematically illustrating major parts of adeveloping unit in accordance with the second embodiment. FIG. 19 is aperspective view illustrating an example vapor supply nozzle providedwith a strip-shaped discharge opening.

In this second embodiment, units other than a developing unit DEV of acoating and developing system may be substantially the same as thosedescribed in the first embodiment with reference to FIGS. 1 to 3.Further, the developing unit DEV in accordance with the secondembodiment may have the same configuration as that of the developingunit DEV of the coating and developing system in accordance with thefirst embodiment. Thus, elaboration of parts in FIG. 18 alreadydescribed in the first embodiment with reference to FIGS. 4 and 5 willbe omitted.

FIG. 18 schematically illustrates nozzle positions when a rinse solutionremoving process is performed after a developing solution supply processand a rinse solution supply process are performed as will be describedbelow with reference to FIG. 20. That is, a developing solution nozzle36 is located outside a cup CP; a rinse nozzle 15 is located at aposition above an approximate center of a wafer W; and a vapor supplynozzle 16 b is located at a position above an approximate edge of thewafer W.

The vapor supply nozzle 16 b is moved above the wafer W from theperiphery of the wafer W toward the center of the wafer W in a spiralshape. The vapor supply nozzle 16 b may have a strip-shaped dischargeopening in a diametric direction of the wafer W. Below, an example vaporsupply nozzle provided with a strip-shaped discharge opening will beexplained with reference to FIG. 19.

As depicted in FIG. 19, the vapor supply nozzle 16 b is formed in, e.g.,a wedge shape such that its width decreases toward a bottom thereof, anda strip-shaped (slit-shaped) discharge opening 16 c for supplying vapor44 of the first processing solution is provided in a bottom surface ofthe vapor supply nozzle 16 b. The discharge opening 16 c is arrangedsuch that its lengthwise direction is oriented toward the center of thewafer W from the periphery thereof.

Further, a temperature control may be performed by using a double pipe16 f including an inner pipe 16 d and an outer pipe 16 e so as to set atemperature of the vapor 44 of the first processing solution to be apreset value depending on the kind of the wafer W, a resist patternand/or the rinse solution. Temperature-controlled hot water suppliedfrom a non-illustrated hot water supply source flows through the outerpipe 6 e, and the vapor 44 of the first processing solution suppliedfrom a vapor supply mechanism 33 flows through the inner pipe 16 d.Further, the temperature-controlled hot water is returned back into thehot water supply source through a return pipe 16 g. The vapor supplynozzle 16 d having the above-described configuration may be used inother embodiments or modification examples.

Now, a developing method in accordance with the second embodiment willbe described with reference to FIGS. 20 to 22B. FIG. 20 provides aflowchart to describe a process sequence. FIGS. 21A to 21D are sideviews and FIGS. 22A and 22B are plane views for illustrating respectiveprocesses.

As depicted in FIG. 20, the developing method in accordance with thesecond embodiment may include a developing solution supply process (stepS31), a rinse solution supply process (step S32), a rinse solutionremoving process (steps S33 to S35) and a drying process (step S36). Therinse solution removing process may include a first removing process(step S33), a second removing process (step S34) and a third removingprocess (step S35).

First, the developing solution supply process (S31) and the rinsesolution supply process (S32) are performed. The developing solutionsupply process (S31) and the rinse solution supply process (S32) may becarried out in the same ways as steps S11 and S12 in accordance with thefirst embodiment, respectively.

Then, the rinse solution removing process (steps S33 to S35) isperformed. In this rinse solution removing process (steps S33 to S35),in the state that the rinse solution 42 is being supplied onto anapproximate center of a wafer W, a rinse solution 42 is scattered whileshifting a position, where the vapor 44 of the first processing solutionis supplied to the wafer W, from a periphery of the wafer W toward theapproximate center of the wafer W.

The first removing process (step S33) is performed first. In the firstremoving process (step S33), in the state that the rinse solution 42 isbeing supplied onto the approximate center of the wafer W, the wafer Wis rotated while supplying the vapor 44 of the first processing solutiononto an approximate edge of the wafer W, so that the rinse solution 42is scattered away.

As illustrated in FIG. 21A, in the state that a rinse nozzle 15 abovethe approximate center of the wafer W is supplying the rinse solution 42onto the wafer W, the wafer W is rotated by a driving motor 54 at arotation speed of, e.g., about 0 rpm to about 200 rpm, desirably, about100 rpm while the vapor supply nozzle 16 b moved to an approximate edgeof the wafer W is supplying the vapor 44 of the first processingsolution to the edge of the wafer W.

As illustrated in FIG. 21A, if the vapor 44 of the first processingsolution 44 is supplied and a concentration, i.e., a pressure of thevapor 44 of the first processing solution 44 increases at theapproximate edge of the wafer W, the rinse solution 42 may be moved to acenter of the wafer W in which the concentration, i.e., the pressure ofthe vapor 44 of the first processing solution is low. As a result, aliquid film of the rinse solution may be recessed at the approximateedge of the wafer W, so that a thickness of the liquid film at theapproximate edge of the wafer W would be reduced, whereas the thicknessof the liquid film at the center portion of the wafer W would beincreased. Then, if the vapor 44 of the first processing solutioncontinues to be supplied, a part of the rinse solution 42 may berepelled on the approximate edge of the wafer W and a part of thesurface of the wafer W may be exposed, so that an interface B betweenthe rinse solution 42 and an atmosphere (vapor 44 of the firstprocessing solution) may be formed on the surface of the wafer W, asillustrated in FIG. 21B. Further, the rinse solution 42 may be rotatablyscattered from the exposed surface of the wafer W at the approximateedge thereof.

Further, in the present embodiment, if the concentration of the vapor 44of the first processing solution increases on the wafer W, the vapor 44of the first processing solution may be mixed with the rinse solution42, resulting in reduction of a surface tension of the rinse solution42. Moreover, if the concentration of the vapor 44 of the firstprocessing solution increases on the wafer W, the vapor 44 of the firstprocessing solution may be mixed with the rinse solution 42 and themixture may reach the surface of the resist pattern 29 on the wafer Wand may hydrophobicize the surface of the resist pattern 29.

In FIGS. 21A to 21D, the vapor 44 of the first processing solutionsupplied from the vapor supply nozzle 16 b is shown to have a certainarea for the purpose of illustration. Since, however, the vapor 44 ofthe first processing solution diffuses as a gas, there exists no clearboundary.

Subsequently, the second removing process (step S34) is performed. Inthe second removing process (step S34), in the state that the rinsesolution 42 is being supplied onto the approximate center of the waferW, the wafer W is rotated, while shifting a position, where the vapor 44of the first processing solution is supplied to the wafer W, from theperiphery of the wafer W toward the center of the wafer W. As a result,the rinse solution 42 is scattered away.

As illustrated in FIG. 21C, in the state that the rinse nozzle 15 abovethe approximate center of the wafer W is supplying the rinse solution 42onto the wafer W and the vapor supply nozzle 16 b is supplying the vapor44 of the first processing solution onto the wafer W, the wafer W isrotated by the driving motor 54 at a rotation speed of, e.g., about 0rpm to about 200 rpm, more desirably, about 100 rpm while the vaporsupply nozzle 16 b is moved toward the approximate center of the waferW.

Further, in the second removing process (step 34), the rinse solution 42may be rotatably scattered from the exposed surface of the wafer W atthe approximate edge thereof as illustrated in FIG. 22A, as in the firstremoving process (step S33). The interface B between the rinse solution42 and the atmosphere (vapor 44 of the first processing solution) ismoved on the surface of the wafer W from the periphery of the wafer Wtoward the center of the wafer W to follow up the movement of the vaporsupply nozzle 16 b.

Then, the third removing process (step S55) is performed. In the thirdremoving process (step S35), when the position where the vapor 44 of thefirst processing solution is supplied to the wafer W reaches theapproximate center of the wafer W, the rinse solution 42 is scatteredaway by rotating the wafer W while slightly moving the rise nozzle 15from the approximate center of the wafer W toward a periphery of thewafer W.

In other words, in the state that the vapor supply nozzle 16 b issupplying the vapor 44 of the first processing solution, the rinsenozzle 15 is slightly moved from the approximate center of the wafer Wtoward the periphery of the wafer W when the vapor supply nozzle 16 breaches the approximate center of the wafer W, as illustrated in FIG.21D. As a result, hydrophobicization of the surface of the resistpattern 29 may be completed on the entire surface of the wafer W, andthe rinse solution 42 to be scattered as a result of the rotation of thewafer W may not be accumulated on the wafer W, but may be scattered offthe wafer W while being rotated on the surface of the wafer W, asdepicted in FIG. 22B.

Thereafter, the drying process (step S36) is performed. In the dryingprocess (step S36), a drying process is performed by rotating the waferW at a preset rotation speed, as in the drying process (step S17) inaccordance with the first embodiment.

After the third removing process (step S35) is performed, the surface ofthe resist pattern 29 is hydrophobicized on the entire surface of thewafer W. Accordingly, a rinse solution supply process may beadditionally performed between the third removing process (step S35) andthe drying process (step S36). Even if the rinse solution is removedafter the additional rinse solution supply process, pattern collapse canbe prevented.

In the second embodiment, a moving speed of the vapor supply nozzle 16 bthat is moved from the edge of the wafer W toward the center of thewafer W is set so as to allow the discharge opening 16 c to reach theapproximate center of the wafer W in about 1 to about 5 seconds in caseof the 12 inch wafer W, for example). Accordingly, by way of example, arotation speed of the wafer W and the moving speed of the nozzle may bedetermined by, e.g., calculation or by previous experiment based on alength of the strip-shaped discharge opening 16 c so as to allow thevapor 44 of the first processing solution to be discharged on the entiresurface of the wafer W without missing parts in a radial directionthereof. At this time, the vapor 44 of the first processing solutiondischarged from the discharge opening 16 c in a strip shape may bediffused on the entire surface of the wafer W without missing parts froman outer side toward an inner side thereof. As a result, ahydrophobicized part of the surface of the resist pattern 29 by thevapor 44 of the first processing solution may be expanded from the edgeof the wafer W toward the center of the wafer W in a spiral shape on theentire surface of the wafer W.

In this second embodiment, the surface of the resist pattern may behydrophobicized by the vapor of the first processing solution includinga hydrophobicizing agent. Accordingly, pattern collapse can besuppressed when the rinse solution is supplied onto a substrate on whichfine resist patterns are formed and then the rinse solution is removedfrom the substrate. Furthermore, by reducing an amount of usage of thehydrophobicizing agent, cost for substrate processing can be reduced.

Further, in the second embodiment, in the state that the rinse solutionis being supplied onto the approximate center of the wafer W, the rinsesolution is scattered and removed while shifting the position, where thevapor of the first processing solution is supplied to the wafer W, fromthe periphery of the wafer toward the center of the wafer. The interfacebetween the rinse solution and the atmosphere is also automaticallymoved on the wafer W from the periphery of the wafer W toward the centerof the wafer W to follow up the movement of the vapor supply nozzle, sothat the interface between the rinse solution and the atmosphere may notbe moved to the center of the wafer W ahead of the vapor supply nozzle.Accordingly, when the rinse solution is supplied onto the substrate onwhich fine resist patterns are formed and when the rinse solution isremoved from this substrate, pattern collapse can be suppressed moresecurely.

Moreover, in the present embodiment, although it has been described thatthe present disclosure is applied to the developing apparatus, thepresent disclosure may not be limited to the developing apparatus butcan be applied to a single-wafer cleaning apparatus that performs acleaning process on a substrate held on a spin chuck. Furthermore, inthe present embodiment, although it has been described that the presentdisclosure is applied to the developing method, the present disclosuremay not be limited to the developing method but can be applied to asingle-wafer cleaning method for performing a cleaning process on asubstrate held on a spin chuck.

Third Embodiment

Now, referring to FIGS. 23 to 25, a developing apparatus and adeveloping method in accordance with a third embodiment will bedescribed.

The developing apparatus in accordance with the third embodiment isdifferent from the developing apparatus in accordance with the firstembodiment in that it includes a nozzle unit having a vapor supplynozzle of an elongated shape and a suction nozzle at a front side in amoving direction of the nozzle unit.

FIG. 23 is a diagram schematically illustrating major parts of adeveloping apparatus in accordance with the third embodiment. FIGS. 24Aand 24B are enlarged views of the nozzle unit.

In the third embodiment, units other than a developing unit DEV of acoating and developing system including the developing apparatus may bethe same as those described in the first embodiment with reference toFIGS. 1 to 3. Further, except the vicinities of the vapor supply nozzle,the developing unit DEV in accordance with the third embodiment may havethe same configuration as that of the developing unit DEV of the coatingand developing system in accordance with the first embodiment. Thus,elaboration of parts in FIG. 23 already described in the firstembodiment with reference to FIGS. 4 and 5 will be omitted.

FIG. 23 schematically illustrates nozzle positions when a rinse solutionremoving process is performed after a developing solution supply processand a rinse solution removing process are performed as will be describedbelow with reference to FIG. 25. That is, a developing solution nozzle36 is located outside a cup CP; a rinse nozzle 15 is located at aposition above an approximate center of a wafer W; and a nozzle unit 160including a vapor supply nozzle is located at a position above anapproximate edge of the wafer W.

As depicted in FIGS. 23 and 24A, the nozzle unit 160 includes a firstdischarge nozzle 161, a first suction nozzle 162, a second dischargenozzle 163, a second suction nozzle 164 and a third discharge nozzle165. The nozzle unit 160 including the respective nozzles is configuredto be movable above the wafer W in a direction C (hereinafter, referredto as a “moving direction”). Further, each of the nozzles may have anelongated shape having a length substantially the same as a diameter ofthe wafer W. The nozzles are arranged in a direction that intersects anelongated direction of the elongated nozzles. Furthermore, the nozzlesmay be configured to be movable all together in the direction(arrangement direction of each nozzle and direction substantiallyparallel with the diametric direction of the wafer W) that intersectsthe elongated direction of the nozzles. Alternatively, as long as apreceding and following relationship to be described below is satisfied,some of the nozzles may be move together, while the others are movedseparately from them. Still alternatively, the nozzles may be configuredto be movable all individually.

The first discharge nozzle 161 supplies vapor 44 of a first processingsolution onto a wafer W. The first discharge nozzle 161 serves as avapor supply unit in accordance with the present disclosure.

The first suction nozzle 162 is configured to be movable on the frontside of the first discharge nozzle 161 in the moving direction C of thenozzle unit 160. The first suction nozzle 162 sucks in a rinse solution42, and serves as a suction unit and a rinse solution removing unit inaccordance with the present disclosure.

The second discharge nozzle 163 is configured to be movable on the rearside of the first discharge nozzle 161 in the moving direction C of thenozzle unit 160. The second discharge nozzle 163 supplies a second rinsesolution 42 b onto the wafer W from which the rinse solution 42 has beenremoved. The second suction nozzle 164 is configured to be movable onthe rear side of the first discharge nozzle 161 in the moving directionC of the nozzle unit 160, and the second suction nozzle 164 sucks andremoves the second rinse solution 42 b supplied on the wafer W. In thisthird embodiment, the second suction nozzle 164 is divided into twonozzles 164 a and 164 b, and these two second suction nozzles 164 a and164 b are respectively provided on the front side and on the rear sideof the second discharge nozzle 163 in the moving direction C of thenozzle unit 160.

The third discharge nozzle 165 is configured to be movable on the rearside of the second discharge nozzle 163 and the second suction nozzle164 in the moving direction C of the nozzle unit 160. The thirddischarge nozzle 165 supplies a gas G onto the wafer W from which thesecond rinse solution 42 b has been removed and thus dries the wafer W.

In order to prevent pattern collapse and reduce an amount of usage ofthe first processing solution 43, the nozzle unit may have only thefirst discharge nozzle 161 and the first suction nozzle 162. That is,the nozzle unit may not include the second discharge nozzle, the secondsuction nozzle and the third discharge nozzle. FIG. 24B illustrates anexample nozzle unit 160 a having only a first discharge nozzle 161 and afirst suction nozzle 162 without having a second discharge nozzle, asecond suction nozzle and a third discharge nozzle.

Further, in this embodiment, a rinse nozzle 15 is provided separatelyfrom the nozzle unit 160. However, the rinse nozzle may be provided on afront side of all nozzles included in the nozzle unit in a direction inwhich the nozzle unit is moved above a wafer W. Accordingly, the rinsenozzle may be included in the nozzle unit. In such a case, the rinsenozzle may have an elongated shape having a length substantially thesame as a diameter of the wafer W like the first discharge nozzle. Adriving motor for rotating a spin chuck 52 may be omitted, asillustrated in FIG. 23.

Now, a developing method in accordance with the third embodiment will beexplained with reference to FIGS. 24A and 25. FIG. 25 provides aflowchart to describe a process sequence.

As described in FIG. 25, the developing method in accordance with thethird embodiment may include a developing solution supply process (stepS41), a rinse solution supply process (step S42), a rinse solutionremoving process (step S43), a second rinse solution removing process(step S44) and a drying process (step S45).

In the aforementioned processes, the rinse solution removing process(step S43) to the drying process (step S45) are mentioned in sequence atpositions on the wafer W. In accordance with the present embodiment,however, while the nozzle unit 160 is being moved above the wafer W fromone side to the other, the processes are performed. The rinse solutionremoving process (step S43) to the drying process (step S45) may beperformed at different positions on the wafer W simultaneously.Accordingly, the following description will be provided at the positionswhere the wafer W is located.

First, the developing solution supply process (step S41) and the rinsesolution supply process (S42) are performed. The developing solutionsupply process (step S41) and the rinse solution supply process (stepS42) may be performed in the same ways as the developing solution supplyprocess (step S11) and the rinse solution supply process (step S12) inaccordance with the first embodiment.

Then, the rinse solution removing process (step S43) is performed. Inthe rinse solution removing process (step S43), while supplying thevapor 44 of the first processing solution from the first elongateddischarge nozzle 161 that is being moved, the rinse solution 42 isremoved by sucking the rinse solution 42 by the first elongated suctionnozzle 162 that is being moved on the front side of the first dischargenozzle 161. The rinse solution removing process (step S43) to the dryingprocess (step S45) are performed without rotating the wafer W.

Further, the third embodiment is described for the case of sucking andremoving the rinse solution while supplying the vapor of the firstprocessing solution onto the wafer W. However, the rinse solution may besucked in after the vapor of the first processing solution is supplied.In such a case, although the rinse solution may not be sucked in whilethe vapor of the first processing solution is being supplied, the rinsesolution may be sucked in and removed under an atmosphere including thevapor of the first processing solution.

Subsequently, the second rinse solution removing process (step S44) isperformed. In the second rinse solution removing process (step S44),while supplying the second rinse solution 42 b such as pure water by thesecond elongated discharge nozzle 163 that is being moved on the rearside of the first discharge nozzle 161, the second rinse solution 42 bis removed by sucking in the second rinse solution 42 b by the secondelongated suction nozzles 164 a and 164 b that is being moved on therear side of the first discharge nozzle 151.

Thereafter, the drying process (step S45) is performed. In the dryingprocess (step S45), a gas such as N₂ is supplied by the third elongateddischarge nozzle 164 that is being moved on the rear side of the seconddischarge nozzle 163 and the second suction nozzle 164 to dry the waferW.

In this third embodiment, the surface of the resist pattern may behydrophobicized by the vapor of the first processing solution includinga hydrophobicizing agent. Accordingly, pattern collapse can besuppressed when the rinse solution is supplied onto a substrate on whichfine resist patterns are formed and then the rinse solution is removedfrom the substrate. Furthermore, by reducing an amount of usage of thehydrophobicizing agent, cost for substrate processing can be reduced.

Furthermore, in the third embodiment as described above, the rinsesolution is removed by sucking in the rinse solution by the suctionnozzle. Accordingly, even in the cases that a processing target objectis not of a circular shape or a center of gravity of the processingtarget object is not located at the center thereof, a process can beperformed without rotating a processing target object, and patterncollapse can be still prevented. Furthermore, by reducing an amount ofusage of the hydrophobicizing agent, cost for substrate processing canbe reduced.

Moreover, in the present embodiment, although it has been described thatthe present disclosure is applied to the developing apparatus, thepresent disclosure may not be limited to the developing apparatus butcan be applied to a single-wafer cleaning apparatus that performs acleaning process on a substrate held on a spin chuck. Furthermore, inthe present embodiment, although it has been described that the presentdisclosure is applied to the developing method, the present disclosuremay not be limited to the developing method but can be applied to asingle-wafer cleaning method for performing a cleaning process on asubstrate held on a spin chuck.

Fourth Embodiment

Now, a developing apparatus and a developing method in accordance with afourth embodiment will be described with reference to FIGS. 26 to 28.

The developing apparatus in accordance with the fourth embodiment isdifferent from the developing apparatus in accordance with the firstembodiment in that a rinse solution is removed by rotating a substrateapproximately in a half-turn and a nozzle unit including a dischargenozzle and a suction nozzle having elongated shapes is positioned tocross an approximate center of the substrate.

FIG. 26 is a diagram schematically illustrating major parts of adeveloping unit in accordance with the fourth embodiment. FIG. 27 is aplane view schematically illustrating a vapor supply nozzle.

FIG. 26 schematically illustrates nozzle positions when a rinse solutionremoving process is performed after a developing solution supply processand a rinse solution supply process are performed as will be describedbelow with reference to FIG. 28. That is, a developing solution nozzle36 is located outside a cup CP; a rinse nozzle 15 is located at aposition above an approximate edge of a wafer W; and a nozzle unit 170including a discharge nozzle 171 is placed at a position above anapproximate center of the wafer W.

As depicted in FIGS. 26 and 27, the nozzle unit 170 includes thedischarge nozzle 171 and two suction nozzles 172. The discharge nozzle171 is an elongated nozzle installed to cross an approximate center ofthe wafer W and provided with an elongated discharge opening 173 havinga length substantially the same as a diameter of the wafer W. Thedischarge nozzle 171 serves as a vapor supply unit in accordance withthe present disclosure.

As depicted in FIGS. 26 and 27, the two suction nozzles 172 arerespectively installed on a front side and on a rear side of thedischarge nozzle 171 in a direction that intersects an elongateddirection of the discharge nozzle 171. Each suction nozzle 172 has anelongated shape and has a length substantially the same as that of thedischarge nozzle 171. Further, each suction nozzle 172 is provided withan elongated suction opening 174 and sucks in and removes a rinsesolution 42 supplied on the wafer W. The suction nozzles 172 serve as asuction unit and a rinse solution removing unit in accordance with thepresent disclosure.

A supply opening 175 for supplying vapor 44 of a first processingsolution into the discharge nozzle 171 is provided above the dischargeopening 173 of the discharge nozzle 171. The vapor 44 of the firstprocessing solution supplied into the discharge opening 173 from a vaporsupply mechanism 33 via the supply opening 175 is diffused to both sidesof the discharge opening 173 in an elongated direction of the dischargeopening 173. As depicted in FIG. 27, the supply opening 175 may not beprovided at an approximate center of the wafer W but may be provided ata position slightly deviated from the approximate center of the wafer Wtoward a periphery of the wafer W in the elongated direction of thedischarge opening 173. With this configuration, a surface of a resistpattern 29 can be uniformly hydrophobicized on the entire surface of thewafer W when the rinse solution 42 is removed by rotating the wafer Wapproximately in a half-turn.

An outlet opening 176 for draining the rinse solution from the suctionnozzle 172 is provided at a position above the suction opening 174 ofthe suction nozzle 172. The rinse solution 42 sucked into the suctionopening 174 may be collected in one place in the elongated direction ofthe suction opening 174 and may be drained through the outlet opening176 by a drain unit 177. As depicted in FIG. 27, the outlet opening 176may be provided at one end of the suction opening 174 in the elongateddirection of the suction opening 174. To elaborate, as shown in FIG. 27,the outlet opening 176 may be provided at a position where the rinsesolution 42 is sucked at the last when the wafer W is rotatedsubstantially in a half-turn. With this configuration, the rinsesolution 42 can be completely removed from the entire surface of thewafer W when the wafer W is rotated approximately in a half-turn.

Now, a developing method in accordance with the fourth embodiment willbe described with reference to FIGS. 27 and 28. FIG. 28 provides aflowchart to describe a process sequence.

As depicted in FIG. 28, the developing method in accordance with thefourth embodiment may include a developing solution supply process (stepS51), a rinse solution supply process (step S52), a film thicknessadjusting process (step S53) and a rinse solution removing process (stepS54).

First, the developing solution supply process (step S51) to the filmthickness adjusting process (step S53) are performed. The developingsolution supply process (step S51) to the film thickness adjustingprocess (step S53) may be performed in the same ways as the developingsolution supply process (step S11) to the film thickness adjustingprocess (step S13) in accordance with the first embodiment.

Then, the rinse solution removing process (step S54) is performed. Inthe rinse solution removing process (step S54), while supplying thevapor 44 of the first processing solution by the elongated dischargenozzle 171 installed to cross the approximate center of the wafer W whenthe wafer W is rotated approximately in a half-turn, the rinse solution42 supplied on the wafer W is removed by sucking the rinse solution 42by the two elongated suction nozzles 172 installed on the front side andon the rear side of the discharge nozzle 171 in the direction thatintersects the elongated direction of the discharge nozzle 171.

As illustrated in FIG. 27, while supplying the vapor 44 of the firstprocessing solution onto the wafer W by the discharge nozzle 171 andsucking in the rinse solution 42 from the wafer W by the suction nozzles172, the wafer W is rotated by a driving motor 54 approximately in ahalf-turn at a low speed of, e.g., about 30 rpm. Accordingly, atpositions where the wafer W is located, the rinse solution 42 can beremoved by sucking the rinse solution 42 by the suction nozzles 172immediately after the vapor 44 of the first processing solution issupplied by the discharge nozzle 171.

Further, the fourth embodiment has been described for the case ofremoving the rinse solution by rotating the wafer approximately in ahalf-turn. However, in case that four discharge nozzles having elongatedshapes may be arranged crosswise and a suction nozzle is installed tosurround the discharge nozzles, the rinse solution may be removed byrotating the wafer W approximately in a quarter-turn. Thus, by designingshapes of the discharge nozzle and the suction nozzle appropriately, therinse solution can be removed by rotating the wafer by a certain angle.

In the fourth embodiment, the surface of the resist pattern may behydrophobicized by the vapor of the first processing solution includinga hydrophobicizing agent. Accordingly, pattern collapse can besuppressed when the rinse solution is supplied onto a substrate on whichfine resist patterns are formed and then the rinse solution is removedfrom the substrate. Furthermore, by reducing an amount of usage of thehydrophobicizing agent, cost for substrate processing can be reduced.

Furthermore, in the fourth embodiment as described above, the rinsesolution is removed by sucking the rinse solution by the suction nozzle.Accordingly, when it is necessary to perform a process without rotatinga processing target object, pattern collapse can be still prevented.Furthermore, by reducing an amount of usage of the hydrophobicizingagent, cost for substrate processing can be reduced.

Moreover, in the present embodiment, although it has been described thatthe present disclosure is applied to the developing apparatus, thepresent disclosure may not be limited to the developing apparatus butcan be applied to a single-wafer cleaning apparatus that performs acleaning process on a substrate held on a spin chuck. Furthermore, inthe present embodiment, although it has been described that the presentdisclosure is applied to the developing method, the present disclosuremay not be limited to the developing method but can be applied to asingle-wafer cleaning method for performing a cleaning process on asubstrate held on a spin chuck.

While various aspects and embodiments have been described herein, otheraspects and embodiments will be apparent to those skilled in the art.The various aspects and embodiments disclosed herein are for thepurposes of illustration and are not intended to be limiting. Therefore,the true scope of the disclosure is indicated by the appended claimsrather than by the foregoing description, and it shall be understoodthat all modifications and embodiments conceived from the meaning andscope of the claims and their equivalents are included in the scope ofthe disclosure.

1. A substrate processing method, comprising: a rinse solution supplyprocess for supplying a rinse solution onto a substrate on which aresist pattern is formed; and a rinse solution removing process forremoving the rinse solution from the substrate in an atmosphereincluding vapor of a first processing solution that hydrophobicizes theresist pattern.
 2. The substrate processing method of claim 1, whereinin the rinse solution removing process, the rinse solution is removedwhile supplying the vapor of the first processing solution onto thesubstrate.
 3. The substrate processing method of claim 1, wherein in therinse solution removing process, the rinse solution is removed byrotating the substrate.
 4. The substrate processing method of claim 3,wherein in the rinse solution removing process, the rinse solution isremoved while supplying the vapor of the first processing solution ontoan approximate center of the substrate.
 5. The substrate processingmethod of claim 4, wherein in the rinse solution removing process, therinse solution is removed while shifting a position, where the vapor ofthe first processing solution is supplied, from a center of thesubstrate toward a periphery of the substrate.
 6. The substrateprocessing method of claim 5, wherein in the rinse solution removingprocess, the rinse solution is removed while shifting the position,where the vapor of the first processing solution is supplied, at a speedcorresponding to a speed at which the rinse solution is scattered andmoved.
 7. The substrate processing method of claim 5, wherein in therinse solution removing process, an amount of light irradiated to andreflected from a surface of the substrate is detected, and the rinsesolution is removed while shifting the position, where the vapor of thefirst processing solution is supplied, based on the detected amount oflight.
 8. The substrate processing method of claim 3, furthercomprising: a second processing solution supply process for supplying asecond processing solution having a smaller surface tension than that ofthe rinse solution onto the substrate on which the rinse solution issupplied, wherein in the rinse solution removing process, the secondprocessing solution is removed.
 9. The substrate processing method ofclaim 3, wherein in the rinse solution removing process, in the statethat the rinse solution is being supplied onto an approximate center ofthe substrate, the rinse solution is scattered away while shifting aposition, where the vapor of the first processing solution is supplied,from a periphery of the substrate toward a center of the substrate. 10.The substrate processing method of claim 1, wherein in the rinsesolution removing process, the rinse solution is removed by sucking therinse solution from the substrate.
 11. The substrate processing methodof claim 10, wherein in the rinse solution removing process, whilesupplying the vapor of the first processing solution by a firstdischarge nozzle that has an elongated shape and is moved above thesubstrate in one direction, the rinse solution is removed by sucking therinse solution by a first suction nozzle that has an elongated shape andis moved on the front side of the first discharge nozzle in the onedirection.
 12. The substrate processing method of claim 11, furthercomprising: a second rinse solution supply process for supplying asecond rinse solution onto the substrate, from which the rinse solutionis removed, by a second discharge nozzle that has an elongated shape andis moved on the rear side of the first discharge nozzle in the onedirection; a second rinse solution removing process for sucking andremoving the second rinse solution, which is supplied on the substratefrom the second discharge nozzle, by a second suction nozzle that has anelongated shape and is moved on the rear side of the first dischargenozzle in the one direction; and a drying process for drying thesubstrate by supplying a gas onto the substrate, from which the secondrinse solution is removed, by a third discharge nozzle that has anelongated shape and is moved on the rear side of the second dischargenozzle and the second suction nozzle in the one direction.
 13. Thesubstrate processing method of claim 10, wherein in the rinse solutionremoving process, while supplying the vapor of the first processingsolution by an elongated discharge nozzle installed to pass anapproximate center of the substrate when the substrate is rotated, therinse solution is removed by sucking the rinse solution by a pluralityof elongated suction nozzles installed on the front side and on the rearside of the discharge nozzle in a direction intersecting an elongateddirection of the discharge nozzle.
 14. A computer readable storagemedium that stores therein a program for implementing a substrateprocessing method as claimed in claim
 1. 15. A substrate processingapparatus comprising: a substrate holder that holds a substrate on whicha resist pattern is formed; a rinse solution supply unit that supplies arinse solution onto the substrate held by the substrate holder; a vaporsupply unit that supplies vapor of a first processing solution, whichhydrophobicizes the resist pattern, onto the substrate on which therinse solution is supplied from the rinse solution supply unit; and arinse solution removing unit that removes the rinse solution from thesubstrate in an atmosphere including the vapor of the first processingsolution supplied from the vapor supply unit.
 16. The substrateprocessing apparatus of claim 15, wherein the rinse solution removingunit removes the rinse solution while the vapor of the first processingsolution is being supplied onto the substrate by the vapor supply unit.17. The substrate processing apparatus of claim 15, wherein the rinsesolution removing unit is a rotating unit that scatters and removes therinse solution by rotating the substrate holder holding the substrate.18. The substrate processing apparatus of claim 17, wherein the rotatingunit removes the rinse solution while the vapor of the first processingsolution is supplied onto an approximate center of the substrate by thevapor supply unit.
 19. The substrate processing apparatus of claim 18,further comprising: a moving unit that moves the vapor supply unit abovethe substrate, wherein the rotating unit removes the rinse solutionwhile a position, where the vapor of the first processing solution issupplied from the vapor supply unit, is being shifted from a center ofthe substrate toward a periphery of the substrate by the moving unit.20. The substrate processing apparatus of claim 19, wherein the rotatingunit removes the rinse solution while the position, where the vapor ofthe first processing solution is supplied from the vapor supply unit, isbeing shifted at a speed corresponding to a speed at which the rinsesolution is scattered and moved.
 21. The substrate processing apparatusof claim 19, further comprising: a detecting unit that detects an amountof light irradiated to and reflected from a surface of the substrate,wherein the rotating unit removes the rinse solution while the position,where the vapor of the first processing solution is supplied, is beingshifted based on the amount of light detected by the detecting unit. 22.The substrate processing apparatus of claim 17, further comprising: asecond processing solution removing unit that supplies a secondprocessing solution, which has a smaller surface tension than that ofthe rinse solution, onto the substrate on which the rinse solution issupplied from the rinse solution supply unit, wherein the rotating unitremoves the second processing solution.
 23. The substrate processingapparatus of claim 17, further comprising: a moving unit that moves thevapor supply unit above the substrate, wherein in the state that therinse solution is being supplied onto an approximate center of thesubstrate by the rinse solution supply unit, the rotating unit removesthe rinse solution while the position, where the vapor of the firstprocessing solution is supplied from the vapor supply unit, is beingshifted from a periphery of the substrate toward a center of thesubstrate by the moving unit.
 24. The substrate processing apparatus ofclaim 15, wherein the rinse solution removing unit is a suction unitthat removes the rinse solution by sucking the rinse solution from thesubstrate.
 25. The substrate processing apparatus of claim 24, whereinthe vapor supply unit is a first discharge nozzle that has an elongatedshape and is configured to be movable above the substrate in onedirection, and the suction unit is a first suction nozzle of anelongated shape that is configured to be movable on the front side ofthe first discharge nozzle in the one direction and that removes therinse solution by sucking the rinse solution while the vapor of thefirst processing solution is being supplied by the first dischargenozzle.
 26. The substrate processing apparatus of claim 25, furthercomprising: a second discharge nozzle of an elongated shape that isconfigured to be movable on the rear side of the first discharge nozzlein the one direction and supplies a second rinse solution onto thesubstrate from which the rinse solution is removed; a second suctionnozzle of an elongated shape that is configured to be movable on therear side of the first discharge nozzle in the one direction and removesthe second rinse solution by sucking the second rinse solution suppliedon the substrate from the second discharge nozzle; and a third dischargenozzle of an elongated shape that is configured to be movable on therear side of the second discharge nozzle and the second suction nozzlein the one direction and dries the substrate by supplying a gas onto thesubstrate from which the second rinse solution is removed.
 27. Thesubstrate processing apparatus of claim 24, further comprising: arotating unit that rotates the substrate holder holding the substrate,wherein the vapor supply unit is a discharge nozzle of an elongatedshape configured to pass the approximate center of the substrate, andthe suction unit is a plurality of elongated suction nozzles that isinstalled on the front side and on the rear side of the discharge nozzlein a direction intersecting an elongated direction of the dischargenozzle and removes the rinse solution by sucking the rinse solutionsupplied on the substrate while the vapor of the first processingsolution is being supplied by the discharge nozzle when the substrateholder holding the substrate is rotated by the rotating unit.